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

Abstract

Provided is a liquid crystal alignment film and a liquid crystal alignment agent that can stably produce a tilt angle from the perpendicular direction and that can achieve high reliability. A liquid crystal alignment agent containing, as a (A) component, a polymer obtained using a monomer represented by the following formula (1), and a solvent. [Chemical 1] (In the formula, the definitions of the respective substituents are shown in the description.)

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 a role in aligning the liquid crystals in a certain direction. Currently, the main liquid crystal alignment films used in industry are formed 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, and polyimide onto a substrate. Furthermore, when the liquid crystals are aligned parallel or obliquely relative to the substrate surface, a surface stretching process using friction is performed after film formation.

[0003] 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.

[0004] 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 and slits, as well as 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).

[0005] 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, as the pretilt angle gradually changes, 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 causes screen burn-in. In particular, to improve transmittance, a pretilt angle must be applied vertically, but to date, no material can stably maintain the pretilt angle applied through photoalignment processing.

[0006] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 3-179323 Patent Document 2: Japanese Patent Application Publication No. 4-281427 Patent Document 3: Japanese Patent No. 4504626 Patent Document 4: Japanese Patent No. 4995267 Summary of the Invention

[0007] The technical problem that the invention aims to solve The inventors conducted research and found that simply adjusting the amount of photo-alignment groups could not stably generate a tilt angle from the vertical direction, nor could it achieve high reliability. The objective of this invention is to provide a liquid crystal alignment film and a liquid crystal alignment agent capable of imparting a pretilt angle from the vertical direction with high reliability.

[0008] Technical solutions for solving technical problems The inventors discovered that, in the following... <x>Inventions with the main purpose of [the invention].

[0009] <x>A liquid crystal alignment agent comprising a polymer obtained by using a monomer shown in formula (1) as component (A), and a solvent.

[0010] [Chemistry 1]

[0011] In equation (1), R 11 Ar is a hydrogen atom or a methyl group, Ar is an aromatic ring that may have substituents, and 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. A may be substituted by a fluorine atom, a chlorine atom, a cyano group, an alkoxy group having 1 to 5 carbon atoms, or a straight-chain or branched alkyl residue. The straight-chain or branched alkyl residue may be substituted by one cyano group or one... In the above halogen atom substitutions, R1 is a single bond, oxygen atom, -COO-, or -OCO-; R2 is a divalent aromatic group, divalent alicyclic group, or divalent heterocyclic group; R3 is a single bond, 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; R4 can be substituted with a fluorine atom; and D represents an oxygen atom, a sulfur atom, or -NR. d - (where R) d R1 and R2 can be denoted by hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, where a is an integer from 0 to 3. When a is 2 or more, multiple R1 and R2 can each independently have the above definition. X and Y can each independently be hydrogen atoms, fluorine atoms, chlorine atoms, cyano groups, or alkyl groups having 1 to 3 carbon atoms, wherein some or all of the hydrogen atoms of the alkyl group can be replaced by fluorine atoms.

[0012] The wavy lines between "C" and "A" and between "C" and "X" indicate the E-type isomer or the Z-type isomer. It should be noted that in this specification, the wavy lines have the same meaning as described above.

[0013] Invention Effects According to the present invention, a liquid crystal alignment film and a liquid crystal alignment agent capable of imparting a pretilt angle starting from the vertical direction and achieving high reliability can be provided. Furthermore, the liquid crystal display element manufactured by the method of the present invention exhibits excellent display characteristics. Detailed Implementation

[0014] The liquid crystal alignment agent of the present invention contains a polymer obtained by using the monomer shown in the following formula (1) as component (A), and a solvent.

[0015] [Chemistry 2]

[0016] In equation (1), R 11 Ar is a hydrogen atom or a methyl group, Ar is an aromatic ring that may have substituents, and 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. A may be substituted by a fluorine atom, a chlorine atom, a cyano group, an alkoxy group having 1 to 5 carbon atoms, or a straight-chain or branched alkyl residue. The straight-chain or branched alkyl residue may be substituted by one cyano group or one... In the above halogen atom substitutions, R1 is a single bond, oxygen atom, -COO-, or -OCO-; R2 is a divalent aromatic group, divalent alicyclic group, or divalent heterocyclic group; R3 is a single bond, 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; R4 can be substituted with a fluorine atom; and D represents an oxygen atom, a sulfur atom, or -NR. d - (where R) d R1 and R2 can be denoted by hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, where a is an integer from 0 to 3. When a is 2 or more, multiple R1 and R2 can each independently have the above definition. X and Y can each independently be hydrogen atoms, fluorine atoms, chlorine atoms, cyano groups, or alkyl groups having 1 to 3 carbon atoms, wherein some or all of the hydrogen atoms of the alkyl group can be replaced by fluorine atoms.

[0017] The wavy lines between "C" and "A" and between "C" and "X" indicate either the E-type isomer or the Z-type isomer.

[0018] The liquid crystal alignment agent of the present invention can satisfy at least one of the following requirements Z1 and Z2.

[0019] Z1: The polymer as component (A) has thermally crosslinking groups A and B.

[0020] Z2: The polymer as component (A) has a thermally crosslinking group A, and also contains a compound with two or more thermally crosslinking groups B in the molecule as component (B).

[0021] The thermally crosslinking group A and thermally crosslinking group B are each independently an organic group selected from carboxyl, protected carboxyl, amino, protected amino, alkoxymethylamide, hydroxymethylamide, hydroxyl, protected hydroxyl, epoxy, oxetyl, thiocyclopropane, isocyanate, and terminal isocyanate groups. The selection is based on the criterion that thermally crosslinking group A and thermally crosslinking group B can undergo a crosslinking reaction by heat. Here, if both thermally crosslinking group A and thermally crosslinking group B are self-crosslinking groups, they can be identical.

[0022] Here, "containing two or more" means, in addition to cases where the molecule contains two or more epoxy groups or two or more identical groups, it also includes cases where the molecule contains two or more different groups, such as combinations of epoxy groups and thiocyclopropane. "Containing two or more" preferably means containing two or more identical groups.

[0023] The polymer contained in the liquid crystal alignment agent of the present invention as component (A) has high light sensitivity, and therefore can exhibit alignment control capability even under low exposure polarized ultraviolet light irradiation.

[0024] Furthermore, the polymer, as component (A), contains a thermally crosslinking group A, and further contains a thermally crosslinking group B. Therefore, even with a short firing time for the liquid crystal alignment agent, a crosslinking reaction involving the polymer, as component (A), can occur. Consequently, when anisotropy is exhibited at the photo-alignment site through a photoreaction, anisotropy is easily retained (stored) in the liquid crystal alignment film, thus improving liquid crystal alignment and exhibiting a pretilt angle for the liquid crystal.

[0025] It should be noted that groups containing the photo-oriented groups of the monomers shown in formula (1) above, thermal crosslinking groups A and B can all become side chains in the polymer, and therefore can be referred to as "side chains" as needed.

[0026] The constituent elements of the present invention will now be described in detail.

[0027] <(A) Ingredients: Specific polymers> [The monomer shown in formula (1)] In this invention, Ar is preferably 1,4-phenylene, 1,3-phenylene, 4,4'-biphenylene, 1,4-naphthylene, 2,6-naphthylene, etc., among the monomers shown in formula (1) above within the molecule.

[0028] As ring A, preferably a benzene ring in which each hydrogen atom can be replaced by the group R5.

[0029] 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.

[0030] R1 is a single bond, an oxygen atom, -COO-, or -OCO-.

[0031] R2 is a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group.

[0032] R3 is a single bond, an oxygen atom, or -COO- or -OCO-.

[0033] 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. R4 can be substituted with a fluorine atom.

[0034] 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.

[0035] a is an integer from 0 to 3.

[0036] In formula (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.

[0037] Examples of divalent alicyclic groups that can be used as R2 include trans-1,4-cyclohexylene and trans-trans-1,4-bicyclohexylene.

[0038] 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.

[0039] R2 is preferably 1,4-phenylene, trans-1,4-cyclohexylene, or trans-trans-1,4-bicyclohexylene.

[0040] 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 the aforementioned 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.

[0041] Examples of monovalent organic groups containing an alicyclic group and having 3 to 40 carbon atoms as R4 include: cholesteryl, cholesteryl, adamantyl, and the following formulas (Alc-1) or (Alc-2) (where R7 is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 20 carbon atoms, and some or all of the hydrogen atoms in the alkyl group having 1 to 20 carbon atoms may be replaced by fluorine atoms). Groups, etc., indicating the bond position.

[0042] [Chemistry 3]

[0043] As the monomer shown in formula (1) above, structures shown in formulas (paa-1-ma1) to (paa-1-ma43) can be cited, but are not limited to these. It should be noted that in the formula, "E" indicates the E-type isomer, and "t" indicates that the cyclohexyl group is trans-isomer. Additionally, R... 11 It represents a hydrogen atom or a methyl group.

[0044] [Chemistry 4]

[0045] [Chemistry 5]

[0046] [Chemistry 6]

[0047] [Chemistry 7]

[0048] From the viewpoint of orientation stability and polymer solubility, the monomer shown in the following formula (HQ) is preferred as the monomer shown in formula (1).

[0049] The compounds represented by the following formula (HQ) are also the subject of this invention.

[0050] In formula (HQ), Q1 is a hydrogen atom or methyl, Q2 is an alkyl group with 3 to 20 carbon atoms or a fluoroalkyl group with 1 to 20 carbon atoms, X and Y are independently hydrogen atoms, fluorine atoms, cyano, methyl, ethyl or trifluoromethyl, Z is a single bond, -O-, -COO- or -OCO-, A and B are independently, depending on the case, pyrimidine-2,5-diyl, pyridin-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4- or 2,6-naphthylene or phenylene substituted with fluorine atoms, chlorine atoms, cyano, alkoxy groups with 1 to 5 carbon atoms, or straight-chain or branched alkyl residues (which are substituted with one cyano or one or more halogen atoms, depending on the case). n is 1 or 2.

[0051] [Chemistry 8]

[0052] This compound, for example, can be manufactured by the method shown in Scheme 1 below.

[0053] (Option 1) In Scheme 1, Q1, Q2, A, B, X, Y, Z, and n are synonyms with the definitions in the above formula (HQ).

[0054] [Chemistry 9]

[0055] The compound represented by formula (HQ-a2) can be synthesized by coupling the compound represented by formula (HQ-a1) and the compound represented by formula (HQ-r1) in the presence of a metal complex catalyst, a ligand, and a base, such as the Heck reaction.

[0056] In the compound represented by formula (HQ-a1), LG is a substituent with deactivation capability, such as halogens like F, Cl, Br, and I; or sulfonate groups such as p-toluenesulfonate (-OSO2C6H4-p-CH3), methanesulfonate (-OSO2CH3), and trifluoromethanesulfonate (-OSO2CF3). From a reactivity point of view, Br, I, and trifluoromethanesulfonate are preferred.

[0057] The amount of the compound represented by formula (HQ-r1) relative to the amount of the compound represented by formula (HQ-a1) is not particularly limited, but is preferably 1.0 equivalent to 10.0 equivalent. More preferably, it is 1.0 equivalent to 4.0 equivalent.

[0058] In this reaction, a suitable metal complex catalyst is used, formed by combining a metal complex and ligands. Typically, palladium or nickel complexes are used as the metal complex, and depending on the reaction, a copper catalyst is preferably used as a co-catalyst.

[0059] As metal complex catalysts, various structures of metal complex catalysts can be used, with so-called low-valent palladium or nickel complexes being preferred, and zero-valent metal complex catalysts with tertiary phosphine or tertiary phosphite as ligands being particularly preferred. Additionally, suitable precursors that readily convert to zero-valent metal complex catalysts in the reaction system can also be used. Furthermore, metal complexes without tertiary phosphine or tertiary phosphite as ligands can be mixed with tertiary phosphine or tertiary phosphite as ligands in the reaction system, thereby generating low-valent metal complex catalysts with tertiary phosphine or tertiary phosphite as ligands in the reaction system.

[0060] Examples of tertiary phosphine or phosphite esters that can serve as ligands include: triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, etc. Metal complex catalysts containing two or more of these ligands are also preferred.

[0061] As metal complex catalysts, it is also preferable to use a combination of palladium complexes that do not contain tertiary phosphites or tertiary phosphites, and metal complexes that do contain tertiary phosphites or tertiary phosphites. In this case, the above-mentioned ligands can be further combined. Examples of palladium complexes that do not contain tertiary phosphites or tertiary phosphites include bis(benzylacetone)palladium, tris(benzylacetone)dipalladium, bis(acetonitrile)dichloropalladium, bis(benzonitrile)dichloropalladium, palladium acetate, palladium chloride, palladium-activated carbon, etc. Furthermore, examples of palladium complexes that contain tertiary phosphites or tertiary phosphites as ligands include (ethylidene)bis(triphenylphosphine)palladium, tetra(triphenylphosphine)palladium, bis(triphenylphosphine)dichloropalladium, etc.

[0062] The amount of these palladium complexes used can be the so-called catalyst amount, preferably 20 mol% or less relative to the compound shown in formula (HQ-a2), particularly preferably 10 mol% or less. Meanwhile, the copper catalyst used as a co-catalyst is preferably a monovalent copper catalyst, such as copper chloride (I), copper bromide (I), copper iodide (I), copper acetate (I), etc.

[0063] As a base, it can use inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, trimethylpyridine, pyrrolidine, piperidine, morpholine, and N-methylmorpholine; and sodium acetate, potassium acetate, and lithium acetate.

[0064] The amount of these bases used relative to the compound shown in formula (HQ-a1) is not particularly limited, but preferably 1.0 to 10.0 equivalents. More preferably 1.0 to 6.0 equivalents.

[0065] As a reaction solvent, any solvent that is stable, inert, and does not hinder the reaction under the given reaction conditions can be used. Suitable solvents include water, alcohols, amines, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et₂O, i-Pr₂O, TBME, CPME, THF, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), and nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be appropriately selected considering the ease of reaction, and one or more solvents can be used alone or in combination. In addition, depending on the circumstances, the above solvents can also be used as water-free solvents by using appropriate dehydrating agents and drying agents.

[0066] There is no particular limitation on the amount of solvent used (reaction concentration), and the reaction can be carried out without using a solvent. However, when a solvent is used, 0.1 to 100 times the mass of the solvent can be used relative to the compound shown in formula (HQ-a1). Preferably, it is 1 to 10 times the mass, and more preferably 2 to 5 times the mass.

[0067] The reaction temperature is preferably selected from a temperature range of -100°C or higher to the boiling point of the reaction solvent used, more preferably -50°C to 200°C, and particularly preferably 20°C to 150°C. The reaction time is 0.1 to 1000 hours, more preferably 0.5 to 100 hours.

[0068] The compound of formula (HQ-a2) obtained by the method shown in the first example of Scheme 1 above is preferably purified by distillation, recrystallization, or column chromatography such as silica gel. It should be noted that recrystallization is preferably carried out at a low temperature whenever possible.

[0069] The compound shown in formula (HQ-a3) can be synthesized by reacting the compound shown in formula (HQ-a2) with the compound shown in formula (HQ-r2).

[0070] In the compound represented by formula (HQ-r2), R-Cl is any compound used for the synthesis of acyl chlorides, such as thionyl chloride (SOCl2), thionyl chloride (SO2Cl2), phosphorus trichloride (PCl3), phosphorus pentachloride (Cl5P), phosphorus oxychloride (POCl3), oxalyl chloride ((COCl)2), etc. Among these, from a general viewpoint, thionyl chloride and oxalyl chloride are preferred.

[0071] The amount of the compound represented by formula (HQ-r2) relative to the amount of the compound represented by formula (HQ-a2) is not particularly limited, but is preferably 1.0 to 3.0 equivalents. More preferably, it is 1.0 to 1.2 equivalents.

[0072] As a reaction solvent, any solvent that is stable, inert, and does not hinder the reaction under the reaction conditions can be used. It can use aprotic polar organic solvents (DMF (N,N-dimethylformamide), DMSO (dimethyl sulfoxide), DMAc (N,N-dimethylacetamide), NMP (N-methyl-2-pyrrolidone), etc.), ethers (Et2O (diethyl ether), i-Pr2O (diisopropyl ether), TBME (tert-butyl methyl ether), CPME (cyclopentyl methyl ether), THF (tetrahydrofuran), dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), and nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be appropriately selected considering factors such as the ease of reaction. In this case, one of the above solvents can be used alone or in combination of two or more. In addition, depending on the circumstances, appropriate dehydrating agents or drying agents can also be used as non-aqueous solvents.

[0073] There is no particular limitation on the amount of solvent used (reaction concentration), and the reaction can be carried out without using a solvent. However, when a solvent is used, 0.1 to 100 times the mass of the solvent can be used relative to the compound shown in formula (HQ-a2). Preferably, it is 1 to 10 times the mass, and more preferably 2 to 5 times the mass.

[0074] To facilitate a more efficient reaction, a suitable base can be used. Commonly used bases include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; organic bases such as sodium tert-butoxy and potassium tert-butoxy; and amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, and trimethylpyridine.

[0075] To facilitate a more efficient reaction, iodine or DMF (N,N-dimethylformamide) can be used as catalysts.

[0076] The amount of these bases or catalysts used is preferably 0.001 to 1.0 equivalents relative to the compound shown in formula (HQ-a2). More preferably, it is 0.001 to 0.01 equivalents.

[0077] The reaction temperature is preferably selected from a temperature range of -100°C or higher to the boiling point of the reaction solvent used, more preferably -50°C to 200°C, and particularly preferably 20°C to 150°C. The reaction time is 0.1 to 1000 hours, more preferably 0.5 to 100 hours.

[0078] The compound of formula (HQ-a3) obtained by the method shown in the above reaction formula is preferably purified by distillation, recrystallization, or column chromatography such as silica gel. It should be noted that recrystallization is preferably carried out at low temperature whenever possible.

[0079] The compound shown in formula (HQ-a4) can be synthesized by condensing the compound shown in formula (HQ-a3) and the compound shown in formula (HQ-r3) in the presence of a base.

[0080] The amount of the compound represented by formula (HQ-a3) relative to the amount of the compound represented by formula (HQ-r3) is not particularly limited, but is preferably 1.0 equivalent to 10.0 equivalent. More preferably, it is 1.0 equivalent to 5.0 equivalent.

[0081] In this reaction, a suitable base is used. Generally, inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate can be used as bases; organic bases such as sodium tert-butoxy and potassium tert-butoxy; and amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, and trimethylpyridine.

[0082] The amount of these bases used is preferably 1.0 to 5.0 equivalents relative to the compound shown in formula (HQ-a3). More preferably, it is 1.0 to 3.0 equivalents.

[0083] As a reaction solvent, any solvent that is stable, inert, and does not hinder the reaction under the reaction conditions can be used. Aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et₂O, i-Pr₂O, TBME, CPME, THF, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), and nitriles (acetonitrile, propionitrile, butyronitrile, etc.) can be appropriately selected considering the ease of reaction. In this case, one or more of the above solvents can be used alone or in combination. Additionally, depending on the circumstances, appropriate dehydrating agents and drying agents can also be used as non-aqueous solvents.

[0084] There is no particular limitation on the amount of solvent used (reaction concentration), and the reaction can be carried out without using a solvent. However, when a solvent is used, 0.1 to 100 times the mass of the solvent can be used relative to the compound shown in formula (HQ-a3). Preferably, it is 1 to 10 times the mass, and more preferably 2 to 6 times the mass.

[0085] The reaction temperature is preferably selected from a temperature range of -100°C or higher to the boiling point of the reaction solvent used, more preferably -50°C to 100°C, and particularly preferably 0°C to 50°C. The reaction time is 0.1 to 1000 hours, more preferably 0.5 to 100 hours.

[0086] In addition to Scheme 1 described above, the compound shown in formula (HQ-a4) can also be manufactured by performing a condensation reaction in the presence of a condensing agent using the compound shown in formula (HQ-a2) and the compound shown in formula (HQ-r3). It should be noted that, as condensing agents, examples include: dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, diisopropylcarbodiimide, 1,1'-carbonyldiimidazole, bis(2-oxo-3-oxazolyl)phosphinic acid chloride, di-2-pyridyl carbonate, triphenyl phosphite, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylureon tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylureon hexafluorophosphate, and diphenyl phosphonate (2,3-dihydro-2-thio-3-benzoxazolyl)phosphonate, but are not limited to these. The amount of condensing agent added is preferably 1.0 to 3.0 equivalents relative to the compound shown in formula (HQ-a2).

[0087] The compound represented by formula (HQ) can be synthesized by condensing the compound represented by formula (HQ-a4) and the compound represented by formula (HQ-r4) in the presence of a base.

[0088] The amount of the compound represented by formula (HQ-r4) relative to the amount of the compound represented by formula (HQ-a4) is not particularly limited, but is preferably 1.0 to 3.0 equivalents. More preferably, it is 1.0 to 2.0 equivalents.

[0089] In this reaction, a suitable base is used. Generally, inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate can be used as bases; organic bases such as sodium tert-butoxy and potassium tert-butoxy; and amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, and trimethylpyridine.

[0090] The amount of these bases used is preferably 1.0 to 4.0 equivalents relative to the compound shown in formula (HQ-a3). More preferably, it is 1.0 to 2.5 equivalents.

[0091] As a reaction solvent, any solvent that is stable, inert, and does not hinder the reaction under the reaction conditions can be used. Aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et₂O, i-Pr₂O, TBME, CPME, THF, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), and nitriles (acetonitrile, propionitrile, butyronitrile, etc.) can be appropriately selected considering the ease of reaction. In this case, one or more of the above solvents can be used alone or in combination. Additionally, depending on the circumstances, appropriate dehydrating agents and drying agents can also be used as non-aqueous solvents.

[0092] There is no particular limitation on the amount of solvent used (reaction concentration), and the reaction can be carried out without using a solvent. However, when a solvent is used, 0.1 to 100 times the mass of the solvent can be used relative to the compound shown in formula (HQ-a4). Preferably, it is 1 to 10 times the mass, and more preferably 2 to 6 times the mass.

[0093] The reaction temperature is preferably selected from a temperature range of -100°C or higher to the boiling point of the reaction solvent used, more preferably -50°C to 100°C, and particularly preferably 0°C to 70°C. The reaction time is 0.1 to 1000 hours, more preferably 0.5 to 100 hours.

[0094] The compound of formula (HQ) obtained by the method shown in the above reaction is preferably purified by distillation, recrystallization, or column chromatography such as silica gel. It should be noted that recrystallization is preferably carried out at low temperatures whenever possible.

[0095] In addition to Scheme 1 described above, a method for manufacturing the compound represented by formula (HQ) can also be achieved by using the compounds represented by formula (HQ-r3) and formula (HQ-r4) to carry out a condensation reaction in the presence of a condensing agent or a base, followed by using the compound represented by formula (HQ-a2) or formula (HQ-a3) to carry out a condensation reaction in the presence of a condensing agent or a base. It should be noted that the aforementioned condensing agent can be used as the condensing agent.

[0096] [Thermocrosslinking group A and thermocrosslinking group B] The thermal crosslinking group A and thermal crosslinking group B are each independently selected from organic groups selected from carboxyl, protected carboxyl, amino, protected amino, alkoxymethylamide, hydroxymethylamide, hydroxy, protected hydroxy, epoxy, oxetyl, thiocyclopropane, isocyanate, and capped isocyanate. The selection is based on the criterion that thermal crosslinking group A and thermal crosslinking group B can undergo a crosslinking reaction by heat. Thermal crosslinking group A and thermal crosslinking group B can be the same as each other.

[0097] The protecting groups of the protected carboxyl group, protected amino group, and protected hydroxyl group in thermal crosslinking group A and thermal crosslinking group B are preferably protecting groups that are removed by heat.

[0098] Examples of acetal protecting groups that protect the carboxyl group include methoxymethyl, ethoxyethyl, and 2-tetrahydropyranyl acetal protecting groups; cyclic alcohol protecting groups, etc.

[0099] Examples of protecting groups for hydroxyl groups include ether-based protecting groups such as methyl, ethyl, tert-butyl, benzyl, p-methoxybenzyl, and triphenylmethyl; acetal-based protecting groups such as methoxymethyl, ethoxyethyl, and 2-tetrahydropyranyl; acyl-based protecting groups such as acetyl, neopentanoyl, benzoyl, and trichloroacetyl; allyl-based protecting groups such as allyl and methylallyl; carbamate-based protecting groups such as tert-butoxycarbonyl; and silyl ether-based protecting groups such as trimethylsilyl, triethylsilyl, and tert-butyldimethylsilyl.

[0100] Examples of protecting groups for amino groups include tert-butoxycarbonyl, benzyloxycarbonyl, 1,1-dimethyl-2-haloethoxycarbonyl, 1,1-dimethyl-2-cyanoethyloxycarbonyl, 9-fluorenylmethoxycarbonyl, allyloxycarbonyl, 2-(trimethylsilyl)ethoxycarbonyl, and other urethane ester protecting groups; amide protecting groups, imide protecting groups, sulfonamide protecting groups, etc.

[0101] Combinations of thermally crosslinking groups A and B include the following: one is a carboxyl group or a protected carboxyl group, and the other is an epoxy group, an oxetyl group, a thiocyclopropane group, or a capped isocyanate group; one is a hydroxyl group or a protected hydroxyl group, and the other is a capped isocyanate group; one is a phenolic hydroxyl group or a phenolic protected hydroxyl group, and the other is an epoxy group, an oxetyl group, or a thiocyclopropane group; one is an amino group or a protected amino group, and the other is a capped isocyanate group; both are N-alkoxymethylamide groups, etc. More preferred combinations include carboxyl and epoxy groups, hydroxyl and capped isocyanate groups, etc.

[0102] To introduce the thermally crosslinking group A into the polymer that is component (A), it is only necessary to copolymerize the monomer having the thermally crosslinking group A.

[0103] Furthermore, when the liquid crystal alignment agent of the present invention satisfies requirement Z1, when manufacturing the polymer as component (A), it is sufficient to copolymerize the monomer having thermal crosslinking group A and the monomer having thermal crosslinking group B.

[0104] Examples of monomers with thermally crosslinking groups include: Monomers containing carboxyl groups, such as acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl) phthalate, mono-(2-(methacryloyloxy)ethyl) phthalate, N-(carboxyphenyl) maleimide, N-(carboxyphenyl) methacrylamide, and N-(carboxyphenyl) acrylamide. Monomers containing hydroxyl groups include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone-2-(acryloyloxy)ethyl acrylate, caprolactone-2-(methacryloyloxy)ethyl acrylate, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone. Monomers containing phenolic hydroxyl groups, such as hydroxystyrene, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)maleimide, and N-(hydroxyphenyl)maleimide. Monomers containing amino groups, such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate. (Methacrylamide) compounds such as N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide, which are substituted with hydroxymethyl or alkoxymethyl. Allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate α - Ethyl glycidyl acrylate, α - n-Propyl glycidyl acrylate, α -glycidyl butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate α 6,7-epoxyheptyl ethyl acrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methyl methacrylate, 3-vinyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide and other monomers containing epoxy groups; 3-(acryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloyloxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)-2,2-difluorooxetane, 3-(acryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-acryloyloxyethyl)oxetane, 3 -(2-Acryloyloxyethyl)-2-ethyloxetane, 3-(2-Acryloyloxyethyl)-3-ethyloxetane, 3-(2-Acryloyloxyethyl)-2-trifluoromethyloxetane, 3-(2-Acryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-Acryloyloxyethyl)-2-phenyloxetane, 3-(2-Acryloyloxyethyl)-2,2-difluorooxetane, 3-(2-Acryloyloxyethyl)-2,2,4-trifluorooxetane, 3-(2-Acryloyloxyethyl)-2,2,4,4-tetrafluorooxetane, 3-(methacryloyloxymethyl)oxetane, 3-(methyl... (methacryloyloxymethyl)-2-methyloxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(methacryloyloxymethyl)-2,2-difluorooxetane, 3-(methacryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-methacryloyloxyethyl)oxetane, 3- Monomers containing oxetyl groups, such as (2-methacryloyloxyethyl)-2-ethyloxetane, 3-(2-methacryloyloxyethyl)-3-ethyloxetane, 3-(2-methacryloyloxyethyl)-2-trifluoromethyloxetane, 3-(2-methacryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-methacryloyloxyethyl)-2-phenyloxetane, 3-(2-methacryloyloxyethyl)-2,2-difluorooxetane, 3-(2-methacryloyloxyethyl)-2,2,4-trifluorooxetane, and 3-(2-methacryloyloxyethyl)-2,2,4,4-tetrafluorooxetane; 2,3-Cyclothiopropyl acrylate or methacrylate, and 2-, 3-, or 4-( β -Cyclothiopropylthiomethyl)styrene, 2-or 3-or 4-( β -cyclothiopropoxymethyl)styrene, 2- or 3- or 4-( β -Cyclothiopropylthio)styrene, 2- or 3- or 4-( β Monomers such as styrene (-cyclothiopropoxy) contain thiocyclopropane; Monomers with terminal isocyanate groups, such as ethyl acrylate-2-(O-(1′-methylpropyleneamino)carboxyamino)acrylate, ethyl acrylate-2-(3,5-dimethylpyrazolyl)carbonylamino)acrylate, ethyl methacrylate-2-(O-(1′-methylpropyleneamino)carboxyamino)acrylate, and ethyl methacrylate-2-(3,5-dimethylpyrazolyl)carbonylamino)acrylate; etc. It should be noted that (meth)acrylamide refers to both acrylamide and methacrylamide.

[0105] Furthermore, in this invention, when obtaining a specific copolymer, in addition to monomers having photo-orientation groups as shown in the above formula (a-1-m), and monomers having thermal crosslinking groups A and thermal crosslinking groups B as needed, other monomers capable of copolymerizing with these monomers may also be used.

[0106] Specific examples of such monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, (meth)acrylamide compounds, and monomers having nitrogen-containing aromatic heterocyclic groups and polymerizable groups.

[0107] Examples of acrylate compounds include: methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracene methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantane acrylate, 2-propyl-2-adamantane acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

[0108] Examples of methacrylate compounds include: methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracene methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantane methacrylate, 2-propyl-2-adamantane methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

[0109] Examples of the aforementioned (meth)acrylamide compounds include acrylamide, methacrylamide, N-methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, etc.

[0110] Examples of the aforementioned vinyl compounds include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, and 3-vinyl-7-oxabicyclo[4.1.0]heptane.

[0111] Examples of the aforementioned styrene compounds include styrene, methylstyrene, chlorostyrene, and bromostyrene.

[0112] Examples of the aforementioned maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0113] The nitrogen-containing aromatic heterocycle can be an aromatic cyclic hydrocarbon containing at least one, preferably one to four, selected from the following formulas [Na] to [Nb] (where Z2 is a straight-chain or branched alkyl group having 1 to 5 carbon atoms).

[0114] [Chemistry 10]

[0115] Specifically, examples include oxazole rings, thiazole rings, pyridine rings, pyrimidine rings, quinoline rings, 1-pyrazoline rings, isoquinoline rings, thiadiazole rings, pyridazine rings, triazine rings, pyrazine rings, phenanthroline rings, quinoxaline rings, benzothiazole rings, oxadiazole rings, and acridine rings. Furthermore, the carbon atoms of these nitrogen-containing aromatic heterocycles may have substituents containing heteroatoms. Pyridine rings are an example of substituents containing such heteroatoms.

[0116] Examples of monomers containing nitrogen-containing aromatic heterocyclic groups and polymerizable groups include: ethyl (meth)acrylate-2-(2-pyridylcarbonyloxy)ester, ethyl (meth)acrylate-2-(3-pyridylcarbonyloxy)ester, and ethyl (meth)acrylate-2-(4-pyridylcarbonyloxy)ester.

[0117] Other monomers used in this invention can be used alone, or two or more monomers can be used in combination.

[0118] The photoreactive site shown in formula (1) above contained in the polymer of component (A) of the liquid crystal alignment agent of the present invention can be used alone, or two or more sites can be used in combination.

[0119] The photoreactive portion shown in formula (1) above is preferably contained in proportions of 5 to 95 mol%, 5 to 60 mol%, or 5 to 40 mol% of all repeating units of the polymer as component (A).

[0120] The polymer of the present invention contains a portion having a thermally crosslinking group, in which thermally crosslinking group A can be used alone, or in combination, two or more portions containing thermally crosslinking group A and thermally crosslinking group B can be used.

[0121] The preferred amount of the site having thermally crosslinkable groups is 5 to 95 mol%, 40 to 95 mol%, or 60 to 95 mol% of all repeating units of the polymer as component (A).

[0122] The content of the structure derived from the other monomers mentioned above preferably includes 0 to 40 mol%, 0 to 30 mol%, or 0 to 20 mol% of all repeating units of the polymer as component (A).

[0123] <Manufacturing methods for specific polymers> The specific polymer of component (A) contained in the liquid crystal alignment agent of the present invention can be obtained by copolymerizing a monomer having the photo-alignment group shown in formula (1) above, a monomer having the thermal crosslinking group A above, and a monomer having the thermal crosslinking group B above, as needed. In addition, it can be copolymerized with the other monomers mentioned above.

[0124] The method for manufacturing the specific polymer of component (A) in this invention is not particularly limited, and commonly used industrial methods can be employed. Specifically, it can be manufactured by cationic polymerization, free radical polymerization, or anionic polymerization of the vinyl monomer. Among these methods, free radical polymerization is particularly preferred from the viewpoint of ease of reaction control.

[0125] As polymerization initiators for free radical polymerization, known compounds such as free radical polymerization initiators and reversible addition-fragmentation chain transfer (RAFT) polymerization reagents can be used.

[0126] Free radical thermal polymerization initiators are compounds that generate free radicals by heating to temperatures above their decomposition temperature. Examples of such free radical thermal polymerization initiators include: peroxide ketones (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), peroxide diacyls (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauryl peroxide, etc.), peroxide ketals (dibutyl peroxycyclohexane, etc.), alkyl peresters (tert-butyl peroxyneodecanate, tert-butyl peroxynepentanoate, tert-amyl peroxy-2-ethylcyclohexane, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), and azo compounds (azobisisobutyronitrile, and 2,2′-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.).

[0127] Such free radical thermal polymerization initiators can be used alone, or in combination of two or more.

[0128] There are no particular limitations on free radical photopolymerization initiators, as long as they are compounds that initiate free radical polymerization through light irradiation. Examples of such free radical photopolymerization initiators include well-known compounds such as benzophenone, Michleichone, 4,4′-bis(diethylamino)benzophenone, xanthonone, thioxanthonone, and isopropyl xanthonone. These compounds can be used alone or in combination of two or more.

[0129] Free radical polymerization has no particular limitations and can use emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, etc.

[0130] The solvent used in the polymerization reaction of the specific polymer that is component (A) is not particularly limited as long as it is a solvent that dissolves the resulting polymer. Specific examples include solvents described in the section on <Solvents> described later, such as N-alkyl-2-pyrrolidones, dialkyl imidazolinones, lactones, carbonates, ketones, compounds shown in formula (Sv-1) and formula (Sv-2), tetrahydrofuran, 1,4-dioxane, dimethyl sulfone, dimethyl sulfoxide, etc.

[0131] These solvents can be used alone or in combination. Furthermore, even solvents that do not dissolve the generated polymers can be mixed with the aforementioned organic solvents to prevent the generated polymers from precipitating.

[0132] In addition, in free radical polymerization, oxygen in the solvent becomes the cause of the polymerization reaction, so organic solvents that are degassed as much as possible are preferred.

[0133] The polymerization temperature during free radical polymerization can be selected from any temperature between 30°C and 150°C, preferably in the range of 50°C to 100°C. Furthermore, the reaction can be carried out at any concentration, with the monomer concentration preferably between 1 and 50% by mass, more preferably between 5 and 30% by mass. The reaction can initially proceed at a high concentration, followed by the addition of an organic solvent.

[0134] In the above-mentioned free radical polymerization reaction, if the ratio of free radical polymerization initiator to monomer is higher, the molecular weight of the resulting polymer will be smaller; if the ratio of free radical polymerization initiator to monomer is lower, the molecular weight of the resulting polymer will be larger. Therefore, the ratio of free radical initiator to monomer is preferably 0.1 to 10 mol%. In addition, various monomer components, solvents, initiators, etc. can be added during polymerization.

[0135] [Polymer Recycling] When recovering the generated polymer from the reaction solution obtained through the above reaction, the reaction solution is added to a poor solvent to precipitate the polymer. Examples of poor solvents for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer precipitated in the poor solvent can be dried under normal or reduced pressure, at room temperature, or by heating after filtration. Furthermore, repeating the process 2 to 10 times to redissolve the precipitated polymer in an organic solvent and then reprecipitate it reduces impurities in the polymer. Examples of poor solvents for this process include alcohols, ketones, and hydrocarbons. Using three or more of these poor solvents further improves purification efficiency and is therefore preferred.

[0136] Regarding the molecular weight of the specific polymer of component (A), taking into account the strength of the resulting coating, the operability during coating formation, and the uniformity of the coating, the weight-average molecular weight determined by gel permeation chromatography (GPC) is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.

[0137] <(B) Component> When the liquid crystal alignment agent used in this invention satisfies requirement Z2, it contains a crosslinking agent as component (B). As component (B), a crosslinking agent having two or more thermally crosslinking groups B can be cited.

[0138] Examples of crosslinking agents as component (B) include epoxy compounds, compounds having two or more amino groups, hydroxymethyl compounds, isocyanate compounds, phenolic plastic compounds, low molecular weight compounds such as end-capped isocyanate compounds, polymers of N-alkoxymethacrylamide, polymers of compounds having epoxy groups, polymers of compounds having isocyanate groups, and other polymers.

[0139] Specific examples of the aforementioned epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromonepentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-phenylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc.

[0140] Examples of compounds having two or more amino groups include alicyclic diamines, aromatic diamines, aromatic-aliphatic diamines, and aliphatic diamines.

[0141] Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, and isophorone diamine.

[0142] Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene, and 1,3-diamino-4-chlorobenzene.

[0143] Examples of aromatic-aliphatic diamines include: 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenylethylamine, 4-aminophenylethylamine, 3-amino-N-methylphenylethylamine, 4-amino-N-methylphenylethylamine, 3-(3-aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methylaminopropyl)aniline, 3-(4-amino... Butyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4-methylaminobutyl)aniline, 3-(5-aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methylaminopentyl)aniline, 6-amino-2-naphthylmethylamine, 6-amino-3-naphthylmethylamine, 2-(6-amino-2-naphthyl)ethylamine, 2-(6-amino-3-naphthyl)ethylamine, etc.

[0144] Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, and 1,9-diamino-5-methylnonane.

[0145] Specific examples of hydroxymethyl compounds include alkoxymethylated glycourea, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

[0146] Specific examples of alkoxymethylated glycoureas include 1,3,4,6-tetra(methoxymethyl)glycourea, 1,3,4,6-tetra(butoxymethyl)glycourea, 1,3,4,6-tetra(hydroxymethyl)glycourea, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetra(butoxymethyl)urea, 1,1,3,3-tetra(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone, etc. Examples of commercially available products include urea compounds (trade names: CYMEL (registered trademark) 1170, POWDER LINK (registered trademark) 1174) manufactured by MITSUI-CYTEC Co., Ltd., methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins (high condensation type, trade names: BECKAMINE (registered trademark) J-300S, BECKAMINE P-955, BECKAMINE N) manufactured by DIC Co., Ltd.

[0147] Specific examples of alkoxymethylated benzoguanidines include tetramethoxymethylbenzoguanidine. Commercially available examples include those manufactured by Allnex (trade name: CYMEL 1123) and Sanwa Chemical Co., Ltd. (trade names: NIKALAC BX-4000, NIKALAC BX-37, NIKALAC BL-60, NIKALAC BX-55H).

[0148] Specific examples of alkoxymethylated melamine include hexamethoxymethyl melamine. Examples of commercially available products include methoxymethyl melamine compounds manufactured by Allnex (trade names: CYMEL 300, CYMEL301, CYMEL303, CYMEL350), butoxymethyl melamine compounds (trade names: MYCOAT 506, MYCOAT 508), methoxymethyl melamine compounds manufactured by Sanwa Chemical (trade names: NIKALAC MW-30, NIKALAC MW-22, NIKALAC MW-11, NIKALAC MS-001, NIKALAC MX-002, NIKALAC MX-730, NIKALAC MX-750, NIKALAC MX-035), and butoxymethyl melamine compounds (trade names: NIKALAC MX-45, NIKALAC MX-410, NIKALAC MX-302).

[0149] Alternatively, the compound can be obtained by condensing melamine compounds, urea compounds, glycourea compounds, and benzoguanamine compounds in which the hydrogen atoms of such amino groups are replaced by hydroxymethyl or alkoxymethyl groups. For example, the high molecular weight compound made from melamine and benzoguanamine compounds described in U.S. Patent No. 6,323,310 can be cited. Commercially available products of the aforementioned melamine compounds include, for example, CYMEL (registered trademark) 303 (manufactured by Allnex Corporation), and commercially available products of the aforementioned benzoguanamine compounds include, for example, CYMEL (registered trademark) 1123 (manufactured by Allnex Corporation).

[0150] Specific examples of isocyanate compounds include VESTANAT B1358 / 100, VESTAGON BF1540 (the above are isocyanurate-modified polyisocyanates manufactured by Evonik Japan Co., Ltd.), Takenate (registered trademark) B-882N, and Takenate B-7075 (the above are isocyanurate-modified polyisocyanates manufactured by Mitsui Chemicals Co., Ltd.).

[0151] The following compounds can be cited as specific examples of phenolic plastic compounds, but phenolic plastic compounds are not limited to the following examples.

[0152] [Chemistry 11]

[0153] Specific examples of compounds having two or more hydroxyalkylamide groups at the molecule's end include Primid (registered trademark) QM-1260 and Primid QM-4510 (both manufactured by EMS-CHEMIE).

[0154] [Chemistry 12]

[0155] Examples of end-capped isocyanate compounds include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (and above, manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, and B-882N (and above, manufactured by Mitsui Chemicals Corporation).

[0156] Furthermore, as a polymer of the aforementioned N-alkoxymethylacrylamide, examples include polymers manufactured using acrylamide compounds or methacrylamide compounds in which N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, etc., are substituted with hydroxymethyl or alkoxymethyl groups.

[0157] Specific examples of such polymers include poly(N-butoxymethacrylamide), copolymers of N-butoxymethacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate. Such polymers have a weight-average molecular weight of 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

[0158] Examples of polymers containing epoxy groups include those made using glycidyl methacrylate, methyl 3,4-epoxycyclohexyl methacrylate, and other compounds containing epoxy groups.

[0159] Specific examples of such polymers include poly(3,4-epoxycyclohexyl methacrylate), poly(glycidyl methacrylate), copolymers of glycidyl methacrylate and methyl methacrylate, copolymers of 3,4-epoxycyclohexyl methacrylate and methyl methacrylate, and copolymers of glycidyl methacrylate and styrene. Such polymers have a weight-average molecular weight of 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

[0160] Examples of polymers containing the aforementioned isocyanate groups include those made using compounds containing isocyanate groups such as ethyl 2-isocyanate methacrylate (Karenz MOI [registered trademark], manufactured by Showa Denko Co., Ltd.), ethyl 2-isocyanate acrylate (Karenz AOI [registered trademark], manufactured by Showa Denko Co., Ltd.), or polymers containing terminal isocyanate groups such as ethyl 2-(O-[1'-methylpropyleneamino]carboxyamino) methacrylate (Karenz MOI-BM [registered trademark], manufactured by Showa Denko Co., Ltd.), ethyl 2-[(3,5-dimethylpyrazolyl)carbonylamino] methacrylate (Karenz MOI-BP [registered trademark], manufactured by Showa Denko Co., Ltd.).

[0161] Specific examples of such polymers include poly(2-isocyanate ethyl acrylate), poly(2-(O-[1'-methylpropyleneamino]carboxyamino) ethyl methacrylate), copolymers of 2-isocyanate ethyl methacrylate and styrene, and copolymers of 2-[(3,5-dimethylpyrazolyl)carbonylamino] ethyl methacrylate and methyl methacrylate. Such polymers have a weight-average molecular weight of 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

[0162] These crosslinking agents can be used alone or in combination of two or more.

[0163] The content of crosslinking agent containing component (B) in the liquid crystal alignment agent used in this invention is preferably 1 to 100 parts by mass based on 100 parts by mass of component (A), and more preferably 1 to 80 parts by mass.

[0164] <(C) Ingredients> The liquid crystal alignment agent of the present invention may also contain a polymer selected from polyamic acid (P') and its imidized polymer (P) as component (C).

[0165] The aforementioned polyamic acid (P') can be obtained through a polymerization reaction between a diamine component and a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride.

[0166] (Diamine) 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 with two or more types. The following diamines can be cited as preferred examples of the diamine (hereinafter also referred to as diamine (p)) used in the manufacture of polyamic acid (P').

[0167] The aromatic diamines (d) indicated by "AXJ" (details described later), p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2,2′-difluoro-4,4′-diaminobiphenyl, 3,3′-difluoro-4,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 3... 3′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 4,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2′-diaminobiphenyl, 2,3′-diaminobiphenyl, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4-amino-2-methylphenyloxy)butane, 1,4-bis(3-aminophenyl)propane 1,5-Diethyl-4-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)decane, 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-Bis(6-amino-2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 4′-[2-(4-aminophenoxy)ethoxy]-[1,1′-biphenyl]-4-amine, 1,4-bis[2-(4-aminophenyl)ethyl]succinate, 1,6-bis[2-(4-aminophenyl)ethyl]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) isophthalate; 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 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; 1,3 -Diamines containing urea bonds, such as 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)pyridine-2,5-diamine, 2-N-(5-aminopyridin-2-yl)pyridine-2,5-diamine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-6-aminobenzimidazole, 5-(1H-benzimidazol-2-yl)phenyl-1,3-diamine and other heterocyclic diamines, or 4,4′-diaminodiphenylamine, 4,4′-diaminodiphenyl-N-methylamine, N,N′-bis(4-aminophenyl)-1,4-benzidine 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 that is deactivated by heating and bonded to a hydrogen atom; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4′-diaminobiphenyl-3-carboxylic acid, 4,4′-diaminodiphenylmethane-3-carboxylic acid, 1,2-bis(4-aminophenyl)ethane-3-carboxylic acid, 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, 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. Aromatic diamines (tn) having a long-chain alkyl group having 12 to 20 carbon atoms, represented by the group "-N(D)-" (D represents a protecting group that is removed and substituted by a hydrogen atom by heating, preferably tert-butoxycarbonyl). Examples include diamines with the group "-N(D)-" (D represents a protecting group that is removed and substituted by a hydrogen atom by heating, preferably tert-butoxycarbonyl).Diamines having siloxane bonds, such as 3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis[3-(p-aminophenylcarbamoyl)propyl]tetramethyldisiloxane; diamines having 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, etc.

[0168] [Chemistry 13]

[0169] 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 - (where 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).

[0170] J represents a monovalent organic group having at least one group selected from alicyclic hydrocarbon groups having 4 to 40 carbon atoms and aromatic hydrocarbon groups having 6 to 40 carbon atoms. In this group, at least one hydrogen atom of the aforementioned alicyclic hydrocarbon group and aromatic hydrocarbon group is replaced by a substituent (v), which is any one of a halogen atom, a halogen-containing alkyl group, a halogen-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) (excluding halogen atoms) may be interrupted by -O-. It should be noted that J may also have at least one group selected from alicyclic hydrocarbon groups and aromatic hydrocarbon groups other than those described above, in addition to the aforementioned alicyclic hydrocarbon groups and aromatic hydrocarbon groups.

[0171] Examples of alkyl groups containing halogen atoms include alkyl groups containing halogen atoms with 1 to 10 carbon atoms.

[0172] Examples of alkoxy groups containing halogen atoms include alkoxy groups with 1 to 10 carbon atoms.

[0173] Examples of alicyclic hydrocarbon groups for J include cyclobutane rings, cyclopentane rings, cyclohexane rings, cyclodecane rings, and steroid skeletons (e.g., cholesteryl groups, lanosteryl 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)

[0174] [Chemistry 14]

[0175] In the formula, X 1 Indicates a single bond, -(CH2) a - (where 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).

[0176] G 1 This indicates a divalent cyclic group selected from phenylene and cyclohexylene. Any hydrogen atom on the above cyclic group may 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.

[0177] 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.

[0178] 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.

[0179] [Chemistry 15]

[0180] Specific examples of the above-mentioned aromatic diamines (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 the above-mentioned structure (S1) or any one of the above 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.

[0181] [Chemistry 16]

[0182] 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.

[0183] When using the above-mentioned aromatic diamine (d) as the above-mentioned diamine (p), it is preferable to use 5 to 95 mol% of the total diamine component used to manufacture polyamic acid (P'), more preferably 10 to 90 mol%.

[0184] (Tetracarboxylic acid dianhydride) 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.

[0185] As a tetracarboxylic acid component that can be used in the synthesis of polyamic acid (P'), it is preferred to include the following tetracarboxylic dianhydrides (hereinafter, also collectively referred to as specific tetracarboxylic dianhydrides).

[0186] It should be noted that the aforementioned tetracarboxylic acid dianhydrides can be used alone or in combination with two or more.

[0187] 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.

[0188] 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.

[0189] The specific tetracarboxylic acid dianhydride used in the above-mentioned proportion relative to 1 mole of all tetracarboxylic acid components used is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more.

[0190] (Synthesis of polyamic acid) 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.

[0191] 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.

[0192] 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.

[0193] Specific examples of the aforementioned organic solvents include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. c 1,3-Butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolinone. Additionally, where 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.

[0194] <End-capping agent> In synthesizing the polyamic acid of this invention, a suitable 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.

[0195] 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.

[0196] 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 diester compounds 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.

[0197] The proportion of the capping agent used is preferably 0.01 to 20 moles, more preferably 0.01 to 10 moles, relative to a total of 100 moles of diamine components used.

[0198] 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.

[0199] <Imidylation of polyamic acid> Examples of methods for imidizing polyamic acid include thermal imidization by directly heating a solution of polyamic acid and catalytic imidization by adding a catalyst to a solution of polyamic acid.

[0200] The temperature for thermal imidization of polyamic acid in solution is 100–400°C, preferably 120–250°C, and preferably the process is carried out while removing water generated by the imidization reaction from the system.

[0201] The chemical (catalyst) imidization of polyamic acid can be carried out by adding an alkaline catalyst and an anhydride to a solution of polyamic acid and stirring the system at a temperature of -20°C to 250°C, preferably 0°C to 180°C.

[0202] The amount of alkaline catalyst is 0.5 to 30 molar times that of the amic acid groups of polyamic acid, preferably 1.5 to 20 molar times, and the amount of acid anhydride is 1 to 50 molar times that of the amic acid groups of polyamic acid, preferably 2 to 30 molar times.

[0203] Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and 1-ethylpiperidine, among which pyridine and 1-ethylpiperidine are preferred because they have moderate basicity for the reaction.

[0204] Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among these, acetic anhydride is preferred because it facilitates purification after the reaction.

[0205] The imidization rate based on catalyst imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0206] In the polyimide resin used in this invention, the dehydration ring-closing rate (imidization rate) of the ammonium acid groups does not necessarily have to be 100%, and can be adjusted arbitrarily according to the application and purpose. It is particularly preferred to be 50% or more.

[0207] Polymer Recycling When recovering and reusing polymer components from a reaction solution of polyamic acid and polyimide, the reaction solution can be precipitated by immersing it in a poor solvent. Examples of poor solvents for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated by immersion in a poor solvent can be recovered by filtration and then dried at room temperature or under normal or reduced pressure.

[0208] Furthermore, by repeating the process 2 to 10 times to redissolve the polymer obtained from precipitation in an organic solvent and then reprecipitate it (the reprecipitation recovery step), impurities in the polymer can be reduced. Using three or more undesirable solvents at this stage, such as alcohols, ketones, or hydrocarbons, further improves purification efficiency and is therefore preferred.

[0209] There are no particular limitations on the organic solvents used to dissolve the resin components in the reprecipitation and recovery process. Specific examples include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, etc. c 1,3-Butyrolactone, 1,3-dimethyl-2-imidazolinone, dipentene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isopentyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, and 4-hydroxy-4-methyl-2-pentanone, etc. Two or more of these solvents can be mixed.

[0210] In the liquid crystal alignment agent of the present invention, when using a polymer of component (C), the content ratio of the polymer of component (A) to the polymer of component (C), in terms of the mass ratio of component (A) to component (C), is preferably 1:99 to 90:10, more preferably 5:95 to 70:30, and even more preferably 10:90 to 50:50.

[0211] [Preparation of Liquid Crystal Alignment Agent] 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 polymer as component (A) as described above, the crosslinking agent as component (B) as needed, and the polyamic acid (P') as component (C) as needed. In this case, the total content of component (A), the crosslinking agent as component (B), and the polyamic acid (P') as component (C) 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, further preferably 1% to 15% by mass, and particularly preferably 1% to 10% by mass.

[0212] Solvent 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 component (A), component (B) as needed, and component (C) as needed. The liquid crystal alignment agent may contain one solvent or a mixture of two or more. Furthermore, even solvents that do not dissolve components (A) and (B) can be used in conjunction with solvents that do dissolve components (A) and (B). In this case, if the surface energy of the solvent that does not dissolve components (A) and (B) is lower than that of the solvent that dissolves components (A) and (B), the liquid crystal alignment agent can be coated well on the substrate, which is therefore preferable.

[0213] Specific examples include water, N-alkyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and other N-alkyl-2-pyrrolidone derivatives, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylcaprolactam, tetramethylurea, 3-methoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 1,3-dimethyl-2-imidazolinone and other dialkylimidazolinone derivatives; c -Butyrolactone, c -Velolactone, d - Lactones such as valproic acid lactone; carbonates such as ethylene carbonate and propylene carbonate; methanol, ethanol, propanol, isopropanol, 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, etc.; compounds shown in formula (Sv-1) and formula (Sv-2), 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, isopentyl butyrate, diisobutylmethanol, diisopentyl ether, etc.

[0214] [Chemistry 17]

[0215] 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 alkylene 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.

[0216] 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 alkylene group of R1 can be straight-chain or branched.

[0217] In formula (Sv-2), the divalent hydrocarbon group having 1 to 6 carbon atoms as Z1 can be alkylene groups having 1 to 6 carbon atoms, for example.

[0218] 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.

[0219] 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. Specific examples of the solvent 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.

[0220] 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.

[0221] 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.

[0222] <Other Ingredients> The liquid crystal alignment agent used in this invention may also contain components other than (A) above, (B) as needed, and (C) above as needed. Examples of such other components include 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 are not limited thereto.

[0223] Crosslinking catalyst To promote the reaction between thermally crosslinking group A and thermally crosslinking group B, a crosslinking catalyst can 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.

[0224] [Compounds that improve film thickness uniformity and surface smoothness] Compounds that can improve film thickness uniformity and surface smoothness include fluorinated surfactants, organosilicon surfactants, and nonionic surfactants.

[0225] 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 Sumitomo 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.).

[0226] 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.

[0227] [Compounds that improve the adhesion between the liquid crystal alignment film and the substrate] 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.

[0228] 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.

[0229] 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.

[0230] 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.

[0231] <Liquid crystal alignment film and liquid crystal display element> The liquid crystal alignment agent of the present invention can be coated and fired 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.

[0232] 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.

[0233] <Coating Formation Process> 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., and these methods can be used depending on the purpose. After being coated onto the substrate by these methods, a coating film can be formed by evaporating the solvent through a heating unit such as a hot plate.

[0234] The firing process after coating with the liquid crystal alignment agent can be carried out at any temperature from 40°C to 300°C, preferably from 40°C to 250°C, and more preferably from 40°C to 230°C.

[0235] The thickness of the coating film formed on the substrate is preferably 5 to 1000 nm, more preferably 10 to 500 nm or 10 to 300 nm. This firing process can be carried out using a hot plate, a hot air circulating furnace, an infrared furnace, or the like.

[0236] Friction treatment can be performed using materials such as rayon cloth, nylon cloth, and cotton cloth.

[0237] <Light Irradiation Process> In one embodiment, alignment processing can be performed using light irradiation, which may include: a step of coating the 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 is in contact with the liquid crystal layer.

[0238] 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.

[0239] 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.

[0240] 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 .

[0241] Liquid crystal display element The liquid crystal display element of the present invention is a liquid crystal display element having a vertically aligned liquid crystal cell. The liquid crystal cell comprises two substrates arranged opposite each other, a liquid crystal layer disposed between the substrates, and a liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention disposed between the substrates and the liquid crystal layer. Specifically, it is a liquid crystal display element having a vertically aligned liquid crystal cell, which is manufactured by: coating the liquid crystal alignment agent of the present invention onto two substrates and firing them to form a liquid crystal alignment film; arranging the two substrates opposite each other with the liquid crystal alignment film; sandwiching a liquid crystal layer between the two substrates; and irradiating with ultraviolet light.

[0242] Thus, it is believed that by using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, and irradiating the liquid crystal alignment film and the liquid crystal layer with ultraviolet light, an interaction occurs between the liquid crystal and the liquid crystal alignment film of the present invention, thereby creating a liquid crystal display element with low residual DC and less prone to burn-in.

[0243] As for the substrate used in the liquid crystal display element of the present invention, there is no particular limitation as long as it is a substrate with high transparency. Generally, it is a substrate on which transparent electrodes for driving liquid crystal are formed. As a specific example, a substrate identical to the substrate described in the liquid crystal alignment film above can be cited.

[0244] The liquid crystal display element of the present invention can also use conventional substrates with electrode patterns and protrusion patterns, but by having a liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention, even when used on a single-sided substrate, it can achieve the desired effect. m m~10 m The system can operate even with line / slit electrode patterns of m, substrates without slit patterns or protrusion patterns on the opposing substrate, which can simplify the manufacturing process of the device and achieve high transmittance.

[0245] In addition, in high-function components such as TFT-type components, components in which transistors are formed between the electrodes used for liquid crystal driving and the substrate can be used.

[0246] In the case of transmissive liquid crystal display elements, the aforementioned substrate is typically used. However, in the case of reflective liquid crystal display elements, if only a single-sided substrate is used, an opaque substrate such as a silicon wafer can also be used. In this case, the electrodes formed on the substrate can also be made of a material such as aluminum that reflects light.

[0247] The liquid crystal alignment film is formed by coating the liquid crystal alignment agent of the present invention onto the substrate and then firing it, as detailed above.

[0248] The liquid crystal composition used in the liquid crystal display element of the present invention can be a nematic liquid crystal having negative dielectric anisotropy. For example, dicyanophenyl liquid crystals, pyridazine liquid crystals, Schiff base liquid crystals, azo oxide liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, terphenyl liquid crystals, etc., can be used. Furthermore, an alkenyl liquid crystal is preferred. Conventionally known liquid crystals can be used as such alkenyl liquid crystals. For example, compounds shown in the following formulas can be cited, but the invention is not limited thereto.

[0249] [Chemistry 18]

[0250] The liquid crystal composition constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited as long as it is a liquid crystal material used in a vertically aligned manner. For example, liquid crystal compositions with negative dielectric anisotropy such as MLC-6608 and MLC-6609 manufactured by Merck can be used. Furthermore, MLC-3022 and MLC-3023 (containing a photopolymerizable compound (RM)) manufactured by Merck, which are liquid crystal compositions containing an alkenyl liquid crystal and having negative dielectric anisotropy, can be used.

[0251] As a method for holding the liquid crystal layer between two substrates, known methods can be cited. For example, the following method can be cited: a pair of substrates having liquid crystal alignment films formed on them are prepared, spacers such as beads are scattered on the liquid crystal alignment film of one substrate, an adhesive is applied around the substrate, and the other substrate is attached with the side having the liquid crystal alignment film forming the inside, and liquid crystal is injected under reduced pressure to seal it.

[0252] Alternatively, a liquid crystal cell can be fabricated using the following method: A pair of substrates with liquid crystal alignment films are prepared; spacers such as beads are dispersed on the liquid crystal alignment film of one substrate, and liquid crystal is then added. Subsequently, the other substrate is bonded to the substrate with the side containing the liquid crystal alignment film facing inwards to achieve sealing. The thickness of the spacers is preferably 1 to 30 mm. m m, more preferably 2 to 10 m m m.

[0253] The step of fabricating a liquid crystal cell by irradiating a liquid crystal alignment film and a liquid crystal layer with ultraviolet light can be performed at any time after the liquid crystal is encapsulated. The amount of ultraviolet light irradiation, for example, is 1–60 J / cm². 2 The preferred value is 40 J / cm. 2 The less ultraviolet radiation, the better it can suppress the decrease in reliability caused by damage to the components that make up the liquid crystal display element.

[0254] The wavelength of the ultraviolet light used is preferably 300–500 nm, more preferably 300–400 nm. It should be noted that the wavelength of the ultraviolet light used in the process of manufacturing the liquid crystal cell is preferably different from the wavelength of the ultraviolet light used in the aforementioned light irradiation process. From the viewpoint of preventing a reverse reaction during the light irradiation process in the process of manufacturing the liquid crystal cell, it is preferable that the wavelength of the ultraviolet light used in the process of manufacturing the liquid crystal cell is longer than the wavelength of the ultraviolet light used in the aforementioned light irradiation process.

[0255] For example, it is preferable that the wavelength of the ultraviolet light used in the above-mentioned light irradiation process is 300-350 nm, and the wavelength of the ultraviolet light used in the process of manufacturing the liquid crystal cell is 350-400 nm. This avoids the problem of damage to photoorientation caused by the reverse reaction of photoorientation groups during the PSA processing after photoorientation treatment.

[0256] Alternatively, ultraviolet irradiation of the liquid crystal alignment film and liquid crystal layer can be performed while applying a voltage and maintaining the electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p.

[0257] In the case of PSA (Polymerization Alignment) method, where polymeric compounds are added to the liquid crystal, if ultraviolet light is irradiated onto the liquid crystal alignment film and liquid crystal layer, the polymeric compounds react to form a polymer. This polymer is used to remember the tilt direction of the liquid crystal molecules, thereby accelerating the response speed of the resulting liquid crystal display element.

[0258] In the above-described photoalignment process, the liquid crystal alignment agent of the present invention undergoes a photoreaction of the photoalignment groups of the polymer as component (A), thereby imparting a tilt angle. Subsequently, during PSA treatment, free radicals generated from the alkenyl liquid crystal in the liquid crystal composition are polymerized, thereby immobilizing the imparted tilt angle. As a result, the durability of the tilt angle of the obtained liquid crystal display element can be improved.

[0259] In addition, the above-mentioned liquid crystal alignment agent is not only useful as a liquid crystal alignment agent for manufacturing liquid crystal display elements with vertical alignment such as PSA type liquid crystal displays and SC-PVA type liquid crystal displays, but can also be suitable for manufacturing liquid crystal alignment films formed by rubbing treatment and photoalignment treatment.

[0260] Example The following examples illustrate the invention in further detail, but the invention is not limited to these examples. The abbreviations of the compounds used and the methods for determining their properties are as follows.

[0261] (Photo-oriented monomer) Among the following photo-oriented monomers, HQ-1 to HQ-11 are included in the monomers shown in formula (1).

[0262] [Chemistry 19]

[0263]

[0264] (Thermocrosslinkable monomer) [Chemistry 20]

[0265] (Tetracarboxylic acid dianhydride) [Chemistry 21]

[0266] (Diamine) [Chemistry 22]

[0267] (Cross-linking agent) [Chemistry 23]

[0268] (Monomer reaction reagents) Et3N: Triethylamine (Polymerization initiator) V-601: Dimethyl 2,2'-azobis(isobutyrate) (solvent) NMP: N-methyl-2-pyrrolidone BCS: Butyl Solvent THF: Tetrahydrofuran DMF: N,N-dimethylformamide DMAc: N,N-dimethylacetamide (Molecular weight determination) The molecular weight of the polymers of polyamic acid and polyimide in the synthesis example was determined using a gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd., and columns (KD-803, KD-805) manufactured by Shodex Co., Ltd., as follows.

[0269] Column temperature: 50℃, eluent: DMF (as additive, lithium bromide monohydrate (LiBr·H2O) 30mmol / L, phosphoric acid·anhydrous crystals (orthophosphoric acid) 30mmol / L, THF 10mL / L), flow rate: 1.0mL / min The standard samples used to prepare the standard curve were: TSK standard polyethylene oxide (molecular weight approximately 900,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight approximately 12,000, 4,000, and 1,000) manufactured by Polymer Laboratories.

[0270] The molecular weight of the polymer obtained from the free radical polymerizable monomer was determined using a room temperature gel permeation chromatography (GPC) apparatus (CBM-20A) (manufactured by Shimadzu Corporation) and a column (Shodex KF-804L and KF-803L in series) (manufactured by Showa Denko Corporation) in the following manner.

[0271] Column temperature: 40℃ Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min Standard samples for preparing the standard curve: Standard polystyrene (molecular weight: 197,000, 55,100, 12,800, 3,950, 1,260) (manufactured by Tosoh Corporation) (Imidification rate determination) The imidization rate in the synthetic example was determined as follows: 20 mg of polyimide powder was placed in an NMR sample tube (manufactured by Kusano Scientific Co., Ltd., NMR sampling tube specifications). f 5) Add 1.0 mL of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS mixture) and sonicate until completely dissolved. The solution was then measured at 500 MHz using a JNW-ECA500 NMR spectrometer manufactured by DATUM, Nippon Electron Ltd. The imidization rate was determined using a proton originating from a structure unchanged before and after imidization as a reference proton. The peak integral value of this proton and the proton peak integral value originating from the NH group of the amic acid appearing around 9.5–10.0 ppm were used to calculate the rate using the following formula. It should be noted that in the following formula, x is the proton peak integral value originating from the NH group of the amic acid, and y is the peak integral value of the reference proton. α The ratio of the number of reference protons to one proton of the NH group of the ammonium acid in the case of polyamic acid (imide content 0%).

[0272] Imidification rate (%) = (1- α (x / y)×100 Synthesis of photoreactive monomers HQ-1 to HQ-11 and AD-1 are novel compounds not disclosed in the literature. The products in the following synthetic examples 1-1 to 1-12 are synthesized by... 1 Identification was performed using H-NMR analysis. The analytical conditions are as follows.

[0273] Apparatus: BRUKER ADVANCE III - 500MHz Solvent for measurement: chloroform - d (CDCl3) Reference substance: tetramethylsilane (TMS) ( d 0.0 ppm for 1H) <Synthesis Example 1 - 1 Synthesis of HQ - 1> [Chemical formula 24]

[0274] <<Synthesis of HQ - 1>> THF (300 g) and DMF (0.05 g) were added to (2E)-3-[4-(trans - 4 - pentylcyclohexyl)phenyl]-2 - acrylic acid (HQ - 1 - 0, 50.3 g, 0.167 mol), and the mixture was stirred in an ice bath at 0 °C. Oxalyl chloride (23.2 g, 0.183 mol) was added dropwise thereto. After the addition was completed, the mixture was stirred at room temperature (25 °C) for 16 hours to allow the reaction to proceed. Stirring was stopped, and the reaction solution was concentrated to obtain HQ - 1 (theoretical yield: 53.3 g).

[0275] <<Synthesis of HQ - 1>> 4 - hydroxyphenyl methacrylate (32.8 g, 0.184 mol), THF (267 g), and Et3N (20.3 g, 0.201 mol) were added, and the mixture was cooled and stirred in an ice bath at 0 °C. A solution of the above - mentioned HQ - 1 - 1 dissolved in THF (160 g) was added dropwise thereto. After the addition was completed, the mixture was stirred at room temperature (25 °C) for 24 hours to allow the reaction to proceed. H2O (1275 g) was added to the reaction solution for water - induced crystallization, and the crystals were filtered out. Methanol (308 g) was added to the obtained crude product, and the mixture was stirred at room temperature (25 °C) for slurry washing. The filtered crystals were dried under reduced pressure, whereby HQ - 1 was obtained (yield: 72.6 g, 0.158 mol, yield: 94% - two steps).

[0276] 1 H - NMR (500 MHz) in CDCl3: d (ppm)=7.85(d,J=16.0Hz,1H),7.51(d,J=8.0Hz,2H),7.27-7.23(m,2H),7.21-7.15(m,4H),6.57(d,J=16.0Hz,1H),6.35(s,1H),5. 76(t,1H),2.53-2.48(m,1H),2.07(s,3H),1.92-1.85(m,4H),1.50-1.42(m,2H),1.38-1.21(m,9H),1.09-1.01(m,2H),0.90(t,3H). <Synthetic Example 1-2: Synthesis of HQ-2> [Chemistry 25]

[0277] HQ-2 was obtained by replacing HQ-1-0 with (E)-3-(4-(((trans, trans)-4'-pentyl-[1,1'-bis(cyclohexane)]-4-carbonyl)oxy)phenyl)acrylic acid (HQ-2-0), otherwise the same procedure as in Synthesis Example 1-1 was followed to obtain HQ-2.

[0278] 1 H-NMR (500MHz) in CDCl3: d (ppm)=7.84(d,J=16.0Hz,1H),7.60(d,J=8.5Hz,2H),7.21-7.13(m,6H),6 .57(d,J=16.0Hz,1H),6.35(s,1H),5.77(s,1H),2.48-2.45(m,1H),2.16(d ,J=11.5Hz,2H),2.07(s,3H),1.87(d,J=11.0Hz,2H),1.78-1.71(m,4H),1 .58-1.50 (m, 2H), 1.32-1.21 (m, 6H), 1.18-0.95 (m, 9H), 0.90-0.82 (m, 5H). <Synthesis Example 1-3: Synthesis of HQ-3> [Chemistry 26]

[0279] HQ-3 was obtained by replacing HQ-1-0 with (E)-3-[4-((trans,trans)-4′-pentyl-[1,1′-bis(cyclohexane)]-4-yl)phenyl]acrylic acid (HQ-3-0), otherwise the same procedure as in Synthesis Example 1-1 was followed to obtain HQ-3.

[0280] 1 H-NMR (500MHz) in CDCl3: d (ppm)=7.85(d,J=15.0Hz,1H),7.51(d,J=10.0Hz,2H),7.27-7.25(m,2H),7.21-7 .14(m,4H),6.58(d,J=15.0Hz,1H),6.35(s,1H),5.76(s,1H),2.52-2.46(m,1H),2 .07 (s, 3H), 1.93 (d, J = 15.0Hz, 2H), 1.87-1.85 (m, 2H), 1.76 (t, 4H), 1.45-1.40 (m ,2H),1.34-1.21(m,6H),1.20-1.11(m,6H),1.10-0.99(m,3H),0.90-0.81(m,5H). <Synthetic Example 1-4: Synthesis of HQ-4> [Chemistry 27]

[0281] HQ-4 was obtained by replacing HQ-1-0 with (E)-3-(4-(((trans, trans)-4'-(4,4,4-trifluorobutyl)-[1,1'-bis(cyclohexane)]-4-carbonyl)oxy)phenyl)acrylic acid (HQ-4-0), otherwise the same procedure as in Synthesis Example 1-1 was followed to obtain HQ-4.

[0282] 1 H-NMR (500MHz) in CDCl3: d (ppm)=7.85(d,J=16.0Hz,1H),7.60(d,J=8.5Hz,2H),7.21-7.13(m,6H), 6.58 (d, J=16.0Hz, 1H), 6.35 (s, 1H), 5.77 (s, 1H), 2.50-2.45 (m, 1H), 2.18 -2.15(m,2H),2.07-2.01(m,5H),1.87(d,J=10.5Hz,2H),1.76(t,4H),1. 60-1.51 (m, 4H), 1.27-1.21 (m, 2H), 1.20-0.96 (m, 7H), 0.92-0.85 (m, 2H). <Synthetic Example 1-5: Synthesis of HQ-5> [Chemistry 28]

[0283] HQ-5 was obtained by replacing HQ-1-0 with (E)-3-[4-(trans-4-pentylcyclohexyl)phenyl]but-2-enoic acid (HQ-5-0), otherwise the same procedure as in Synthesis Example 1-1 was followed to obtain HQ-5.

[0284] 1 H-NMR (500 MHz) in CDCl3: d (ppm) = 7.49 (d, J = 8.5 Hz, 2H), 7.25 (d, J = 8.5 Hz, 2H), 7.18 - 7.14 (m, 4H), 6.36 - 6.35 (m, 2H), 5.76 (t, 1H), 2.63 (d, J = 1.0 Hz, 3H), 2.54 - 2.47 (m, 1H), 2.06 (s, 3H), 1.92 - 1.87 (m, 4H), 1.51 - 1.42 (m, 2H), 1.36 - 1.21 (m, 9H), 1.10 - 1.02 (m, 2H), 0.90 (t, 3H). <Synthesis Example 1-6 Synthesis of HQ-6> [Chemical Formula 29]

[0285] Using (E)-3-[4-(trans-4-propylcyclohexyl)phenyl]acrylic acid (HQ-6-0) instead of HQ-1-0, and carrying out the same procedure as in Synthesis Example 1-1, HQ-6 was obtained.

[0286] 1 H-NMR (500 MHz) in CDCl3: d (ppm) = 7.85 (d, J = 16.0 Hz, 1H), 7.51 (d, J = 8.0 Hz, 2H), 7.27 - 7.23 (m, 2H), 7.21 - 7.15 (m, 4H), 6.57 (d, J = 16.0 Hz, 1H), 6.35 (s, 1H), 5.76 (t, 1H), 2.54 - 2.48 (m, 1H), 2.07 (s, 3H), 1.91 - 1.85 (m, 4H), 1.50 - 1.42 (m, 2H), 1.39 - 1.28 (m, 3H), 1.27 - 1.20 (m, 2H), 1.10 - 1.01 (m, 2H), 0.90 (t, 3H). <Synthesis Example 1-7 Synthesis of HQ-7> [Chemical Formula 30]

[0287] <<Synthesis of HQ-7-0>> Charge 1-bromo-2-fluoro-4-(trans-4-pentylcyclohexyl)phenyl (32.7 g, 100 mmol), acrylic acid (10.8 g, 150 mmol), tripropylamine (43.0 g, 300 mmol), and DMAc (100 g). After purging with nitrogen, charge palladium acetate (0.45 g, 2.0 mmol) and tris(ortho-tolyl)phosphine (1.2 g, 4.0 mmol), and stir at 100 °C. After completion of the reaction, pour the reaction solution into 1N hydrochloric acid aqueous solution (400 g), filter the precipitate, and dry. Add THF (200 g) to the obtained crude product, dissolve at 45 °C, filter the insoluble matter, and concentrate the filtrate. Add ethyl acetate (250 g) to the obtained crude product, dissolve at 50 °C, cool to 0 °C, filter, and dry to obtain HQ-7-0 (yield: 23.2 g, 0.073 mol, yield: 73%).

[0288] <<Synthesis of HQ-7>> Use (E)-3-(2-fluoro-4-((1s,4r)-4-propylcyclohexyl)phenyl)acrylic acid (HQ-7-0) instead of HQ-1-0, and carry out the same procedure as in Synthesis Example 1-1 to obtain HQ-7.

[0289] 1 H-NMR (500 MHz) in CDCl3: d (ppm) = 7.94 - 7.97 (d, 1H), 7.48 - 7.50 (t, 1H), 7.15 - 7.21 (m, 4H), 7.03 - 7.05 (d, 1H), 6.96 - 6.99 (d, 1H), 6.66 - 6.69 (d, 1H), 6.35 (s, 1H), 5.76 (s, 1H), 2.47 - 2.52 (t, 1H), 2.07 (s, 3H), 1.87 - 1.91 (m, 4H), 1.39 - 1.47 (m, 2H), 1.21 - 1.34 (m, 9H), 1.01 - 1.08 (m, 2H), 0.88 - 0.91 (t, 3H). <Synthesis Example 1-8 Synthesis of HQ-8> [Chemical Formula 31]

[0290] Use (E)-2-methyl-3-(4-((1s,4r)-4-pentylcyclohexyl)phenyl)acrylic acid (HQ-8-0) instead of HQ-1-0, and carry out the same procedure as in Synthesis Example 1-1 to obtain HQ-8.

[0291] 1 H-NMR (500 MHz) in CDCl3: d (ppm) = 7.88 (s, 1H), 7.40 - 7.42 (d, 2H), 7.26 - 7.28 (d, 2H), 7.15 - 7.20 (m, 4H), 6.35 (s, 1H), 5.76 (s, 1H), 2.48 - 2.52 (t, 1H), 2.25 (s, 3H), 2.07 (s, 3H), 1.88 - 1.92 (m, 4H), 1.35 - 1.50 (m, 2H), 1.22 - 1.33 (m, 9H), 1.03 - 1.10 (m, 2H), 0.89 - 0.91 (t, 3H). <Synthesis Example 1-9 Synthesis of HQ-9> [Chemical Formula 32]

[0292] <<Synthesis of HQ-9-0>> Charge 1-bromo-2-fluoro-4-(trans-4-pentylcyclohexyl)phenyl (19.6 g, 60 mmol), methacrylic acid (20.7 g, 240 mmol), tripropylamine (51.6 g, 360 mmol), DMAc (60 g). After purging with nitrogen, charge palladium acetate (0.27 g, 1.2 mmol) and tris(ortho-tolyl)phosphine (0.73 g, 2.4 mmol), and stir at 130 °C. After completion of the reaction, pour the reaction solution into 1N hydrochloric acid aqueous solution (240 g), filter out the precipitate, and dry. Add THF (160 g) to the obtained crude product, dissolve at 45 °C, filter out the insoluble matter, and concentrate the filtrate. Add ethyl acetate (120 g) to the obtained crude product, dissolve at 50 °C, cool to 0 °C, filter and dry to obtain HQ-9-0 (yield: 6.1 g, 0.018 mol, yield: 30%).

[0293] <<Synthesis of HQ-9>> Use (E)-3-(2-fluoro-4-((1s,4r)-4-pentylcyclohexyl)phenyl)-2-methylacrylic acid (HQ-9-0) instead of HQ-1-0, and carry out the same procedure as in Synthesis Example 1-1 to obtain HQ-9.

[0294] 1 H-NMR (500 MHz) in CDCl3: d (ppm) = 7.92 (s, 1H), 7.33 - 7.36 (t, 1H), 7.15 - 7.21 (m, 4H), 7.03 - 7.05 (d, 1H), 6.96 - 6.99 (d, 1H), 6.35 (s, 1H), 5.76 (s, 1H), 2.47 - 2.52 (t, 1H), 2.17 (s, 3H), 2.07 (s, 3H), 1.88 - 1.93 (t, 4H), 1.39 - 1.48 (m, 2H), 1.21 - 1.34 (m, 9H), 1.01 - 1.09 (m, 2H), 0.89 - 0.91 (t, 3H). <Synthesis Example 1 - 10 Synthesis of HQ - 10> [Chemical Formula 33]

[0295] Using 4 - hydroxyphenyl acrylate instead of 4 - hydroxyphenyl methacrylate, and carrying out the same procedure as in Synthesis Example 1 - 1, HQ - 10 was obtained.

[0296] 1 1H - NMR (500 MHz) in CDCl3: d (ppm) = 7.83 - 7.86 (d, 1H), 7.51 - 7.52 (d, 2H), 7.25 - 7.27 (m, 2H), 7.16 - 7.21 (m, 4H), 6.56 - 6.63 (m, 2H), 6.30 - 6.35 (m, 1H), 6.01 - 6.03 (d, 1H), 2.48 - 2.52 (t, 1H), 1.88 - 1.91 (m, 4H), 1.44 - 1.48 (m, 2H), 1.24 - 1.33 (m, 9H), 1.04 - 1.07 (m, 2H), 0.89 - 0.91 (t, 3H). <Synthesis Example 1 - 11 Synthesis of HQ - 11> [Chemical Formula 34]

[0297] <<Synthesis of HQ - 11 - 1>> The process was carried out in the same manner as in Synthesis Example 1-1 up to HQ-1-1. THF (120 g) and tert-butylhydroquinone (33.2 g, 0.200 mol) were added to HQ-1-1 (21.2 g), and the mixture was stirred at 25°C. Et3N (11.5 g, 0.113 mol) was added dropwise, and the mixture was stirred at 25°C for 21 hours after the addition was complete. Ion-exchanged water (120 g) was added to the reaction mixture and stirred to dissolve the precipitated Et3N·HCl. Ethyl acetate (120 g) was added, and the mixture was transferred to a separatory funnel for extraction with ethyl acetate to remove the aqueous phase. The organic phase was concentrated to obtain the crude product. Methanol (90 g) was added to the obtained solid, and the mixture was stirred and washed at 25°C. The filtered solid was dried to obtain HQ-11-1.

[0298] 1 H-NMR (500MHz) in CDCl3: d (ppm)=7.83(d,J=16.0Hz,1H),7.50(d,J=8.2Hz,2H),7.25(d,J=8.2Hz,2H),7.02(d,J=2.8Hz,1H),6.88-6.86(m,1H),6.66(d,J =8.5Hz,1H),6.57(d,J=16.0Hz,1H),2.52-2.48(m,1H),1.91-1.87(m,4H),1.53-1.21(m,21H),1.09-1.02(m,2H),0.90(t,3H). THF (30 g) and Et3N (2.48 g, 0.0245 mol) were added to HQ-11-1 (6.00 g, 0.0111 mol), and the mixture was stirred at room temperature (25 °C). Methacrylamide chloride (2.33 g, 0.0223 mol) was added dropwise, and the mixture was stirred at 50 °C for 3 hours after the addition was complete. Since residual raw materials remained, Et3N (1.13 g, 0.0111 mol) and methacryloyl chloride (1.17 g, 0.0111 mol) were added separately, and the mixture was heated and stirred at 60 °C for 17 hours, resulting in the disappearance of the raw materials. Ion-exchanged water (90 g) was added to the reaction solution for hydration crystallization, and the solution was filtered to obtain the crude product. Methanol (35 g) was added to the crude product, and the mixture was stirred at room temperature (25 °C), the slurry was washed, and the solid was filtered off. THF (16g) was added to the obtained solid and dissolved completely. Heptane (64g) was added and the THF was concentrated. The precipitated white solid was filtered out and dried to obtain HQ-11.

[0299] 1 H-NMR (500MHz) in CDCl3: d (ppm)=7.84(d,J=16.0Hz,1H),7.51(d,J=8.2Hz,2H),7.26(d,J=8.2Hz,2H),7.18(d,J=2.6Hz,1H),7.07-7.02(m,2H),6.58(d,J=16.0Hz,1 H),6.37(s,1H),2.54-2.48(m,1H),2.10(s,3H),1.92-1.87(m,4H),1 .50-1.42(m,2H),1.38-1.21(m,19H),1.10-1.02(m,2H),0.90(t,3H). <Synthetic Example 1-12 Synthesis of AD-1> [Chemistry 35]

[0300] The same procedure as in Synthesis Example 1-1 was followed, except that 3-hydroxyadamantane-1-ylmethacrylate was used instead of 4-hydroxyphenylmethacrylate, to obtain AD-1.

[0301] 1 H-NMR (500MHz) in CDCl3: d (ppm)=7.54-7.57(d,1H),7.42-7.43(d,2H),7.20-7.22(d,2H),6.28- 6.31(d,1H),6.02(s,1H),5.49(s,1H),2.58(s,2H),2.45-2.50(t,1H), 2.39 (s, 2H), 2.10-2.22 (m, 8H), 1.87-1.89 (m, 7H), 1.58 (s, 1H), 1.40- 1.48 (m, 2H), 1.21-1.34 (m, 10H), 1.00-1.08 (m, 2H), 0.88-0.91 (t, 3H). [Polymer Synthesis] <Synthesis example 2-1> In a 100 mL four-necked flask, HQ-1 (2.30 g, 5.00 mmol), MA-1 (1.94 g, 22.5 mmol), MA-2 (3.20 g, 22.5 mmol), and V-601 (0.576 g, 2.50 mmol), serving as free radical polymerization monomers, were dissolved in THF (30 g) to prepare a monomer mixed solution. After degassing the mixed solution using a diaphragm pump, the solution was heated and stirred at 60°C for 18 hours to obtain polymer solution PM-1. The weight-average molecular weight (Mw) was determined to be 43,000 using GPC with a polystyrene conversion, and the molecular weight distribution (Mw / Mn) was 2.4.

[0302] <Synthesis Examples 2-2 to 2-17> As shown in Table 1 below, the types and molar ratios of the monomers used were changed, but the same operation as in Synthesis Example 2-1 was performed, thereby obtaining polymer solutions PM-2 to 18.

[0303] [Table 1]

[0304] <Synthesis example 3-1> In a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, DA-1 (3.97 g, 20.00 mmol), DA-2 (7.27 g, 30.00 mmol), DA-3 (3.04 g, 20.00 mmol), DA-5 (12.3 g, 30.00 mmol), and NMP (106 g) were added and stirred at room temperature while introducing nitrogen gas to dissolve the substances. Subsequently, CA-1 (18.8 g, 96.00 mmol) and NMP (75.3 g) were added under ice-cold conditions, and the mixture was stirred at 40 °C for 12 hours to obtain a solution of polyamic acid (PAA-1) with a solid content of 20% by mass (viscosity: 833 mPa·s).

[0305] <Synthesis Examples 3-2, 3-3> As shown in Table 2 below, the types and molar ratios of the monomers used were changed, and the same operation as in Synthesis Example 3-1 was performed to obtain polymer solutions PAA-2 and PAA-3.

[0306] <Synthesis example 3-4> In a 300 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, DA-3 (7.32 g, 48.1 mmol), DA-2 (8.70 g, 35.9 mmol), DA-4 (13.7 g, 35.9 mmol), CA-2 (6.00 g, 24.0 mmol), and NMP (175 g) were added, and the mixture was stirred at 60 °C for 5 hours while introducing nitrogen gas. Afterward, the mixture was cooled to 15 °C, and then CA-1 (13.4 g, 68.5 mmol), CA-3 (5.22 g, 23.9 mmol), and NMP (43.8 g) were added. The mixture was stirred at 40 °C for 10 hours to obtain a polyamic acid solution with a solid content of 20% by mass (viscosity: 850 mPa·s).

[0307] In a 300 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 210 g of the obtained polyamic acid solution was measured out. NMP was added at a solid content concentration of 6.5% by mass, along with acetic anhydride (36.4 g) and pyridine (11.3 g). The mixture was stirred at room temperature (25 °C) for 30 minutes, and then reacted at 75 °C for 2.5 hours. The reaction solution was then added to methanol (2940 mL), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 °C to obtain polyimide powder. The imidization rate of the polyimide powder was 75%.

[0308] NMP was added to the obtained polyimide powder (2.00 g) to make the solid component concentration reach 12% by mass, and the mixture was stirred at 70°C for 2 hours to dissolve it, thus obtaining a polyimide (PI-1) solution.

[0309] The specifications of the polyamic acid and polyimide obtained in the above synthetic examples 3-1 to 3-4 are shown in Table 2. In Table 2, the values ​​for the tetracarboxylic acid components indicate the amount (mole parts) of each compound used relative to 100 moles of the total amount of tetracarboxylic acid components used in each polymerization step. The values ​​for the diamine components indicate the amount (mole parts) of each compound used relative to 100 moles of the total amount of diamine components used in each polymerization step.

[0310] [Table 2]

[0311] (Example 1) BCS was added to the polymer solution (PM-1) obtained in Synthesis Example 2-1, and THF was removed by vacuum distillation, thereby obtaining a BCS solution of PM-1 with a solid content concentration of 20% by mass. Next, NMP and BCS as solvents were added to the BCS solution of PM-1, and the mixture was stirred at room temperature to obtain liquid crystal alignment agent AL-1. The solvent composition of liquid crystal alignment agent AL-1 was NMP:BCS = 60:40 (mass ratio), and the polymer solid content concentration was 4% by mass.

[0312] (Example 2) In the BCS solution of PM-1 obtained in Example 1, CL-1 as a crosslinking agent and NMP and BCS as solvents were added and stirred at room temperature to obtain liquid crystal alignment agent AL-2. The solvent composition of liquid crystal alignment agent AL-2 was NMP:BCS=60:40 (mass ratio), the polymer solid component concentration was 4% by mass, and CL-1 was 10 parts by mass relative to 100 parts by mass of polymer solid component.

[0313] (Example 3) In the BCS solution of PM-1 obtained in Example 1, a solution of polyamic acid PAA-1 obtained in Synthesis Example 3-1, along with NMP and BCS as solvents, was added, and the mixture was stirred at room temperature to obtain liquid crystal alignment agent AL-3. The solvent composition of liquid crystal alignment agent AL-3 was NMP:BCS = 60:40 (mass ratio), the polymer solids concentration was 4% by mass, and the polymer solids ratio was PM-1:PAA-1 = 15:85 (mass ratio).

[0314] (Examples 4-27 and Comparative Examples 1-5) As shown in Table 3, the polymer solution and the type of additives used were changed, but otherwise the same procedure was followed as in Examples 1 to 3, thereby obtaining liquid crystal alignment agents (AL-4) to (AL-28) and (AL-R1) to (AL-R6).

[0315] [Table 3]

[0316] <Fabrication of Liquid Crystal Display Components> The liquid crystal alignment agents (AL-1) to (AL-28) obtained in the examples and the liquid crystal alignment agents (AL-R1) to (AL-R6) obtained in the comparative examples were respectively processed using a fine pore size of 1 m A membrane filter of size m is used for pressurized filtering.

[0317] The obtained solution was spin-coated onto the ITO side of a glass substrate with a transparent electrode containing an ITO film. After drying at 70°C for 90 seconds, it was fired at 200°C for 30 minutes to form a liquid crystal alignment film with a thickness of 100 nm.

[0318] 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.

[0319] Prepare two substrates as described above, and disperse 4... m After forming spacer microspheres, a sealant (Mitsui Chemicals, XN-1500T) is applied. Next, another substrate is bonded so that the liquid crystal alignment film surfaces face each other and are aligned at 180°. The sealant is then heat-cured at 120°C for 90 minutes, thus creating an empty cell. Liquid crystal (Merck, MLC-3022) is injected into this empty cell using a depressurized injection method to obtain a liquid crystal display element.

[0320] <Evaluation> (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, the case with no light leakage, no domain region formation or other orientation defects, and uniform liquid crystal driving when voltage is applied to the liquid crystal cell was evaluated as "good", and the other cases were evaluated as "poor". The evaluation results are shown in Table 4.

[0321] (Pre-tilt angle) For the liquid crystal display elements fabricated above, the pretilt angle of the liquid crystal cells was measured using an AxoScan manufactured by Axometrics, employing the Mueller matrix method. The evaluation results are shown in Table 4.

[0322] (Evaluation of changes in tilt angle) After measuring the pretilt angle, a 15V DC voltage was applied to the liquid crystal cell, and the tilt angle was measured again after 24 hours. The change in tilt angle was then calculated. The evaluation results are shown in Table 4. The smaller the tilt angle change, the better the image retention characteristics. Specifically, the tilt angle change is less than 0.05, preferably less than 0.04, and most preferably less than 0.03.

[0323] (Voltage retention rate (VHR)) The VHR evaluation is performed by applying a 4V voltage to the liquid crystal cell fabricated above at a temperature of 60°C. m s, measure the voltage after 16.67ms, and calculate how much of the voltage can be maintained as the voltage holding rate.

[0324] 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.

[0325] [Table 4]

[0326] As shown in Table 4, based on the comparison between Examples 1 and 11-19, 22-24, 27-28 and Comparative Example 1, the liquid crystal alignment film obtained by using a liquid crystal alignment agent with an aromatic group directly bonded to the polymerizable functional group exhibits less tilt angle variation, excellent image retention characteristics during AC driving, and excellent voltage retention characteristics. On the other hand, the liquid crystal alignment film obtained by using a liquid crystal alignment agent with an aromatic group not directly bonded to the polymerizable functional group exhibits greater tilt angle variation and poor image retention characteristics during AC driving.

[0327] Furthermore, based on the comparison between Example 1 and Comparative Example 5, the voltage retention rate of the liquid crystal alignment film obtained by using a liquid crystal alignment agent with a photo-alignment monomer that does not have a methacryloyl group on its polymeric functional group is poor.

[0328] Furthermore, based on the comparison between Example 2 and Comparative Example 2, even when a crosslinking agent is introduced into this alignment agent, when using a photoalignment monomer with aromatic groups directly bonded to polymeric functional groups, it is possible to obtain a liquid crystal alignment film with minimal tilt angle change, excellent image retention characteristics during AC driving, and excellent voltage retention characteristics.

[0329] Furthermore, based on the comparison with Examples 3-10 and 20-21, 25-26, and Comparative Examples 3 and 4, it can be seen that even if the alignment agent is changed to a polymer blend with polyamic acid or polyimide that does not contain photo-alignment groups, the same can be obtained. When using a photo-alignment monomer with aromatic groups directly bonded to polymeric functional groups, a liquid crystal alignment film with less tilt angle change, excellent image retention characteristics during AC driving, and excellent voltage retention characteristics can be obtained.

[0330] Industrial availability 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.< / x> < / x>

Claims

1. A liquid crystal alignment agent, characterized in that, Contains: a polymer obtained using the monomer shown in formula (1) below as component (A), and a solvent. In equation (1), R 11 Ar is a hydrogen atom or a methyl group, and Ar is an aromatic ring with or without substituents; 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, and A is or is not substituted by a fluorine atom, a chlorine atom, a cyano group, an alkoxy group having 1 to 5 carbon atoms, or a straight-chain or branched alkyl residue, which is or is not substituted by one cyano group or one... More than one halogen atom is substituted; R1 is a single bond, oxygen atom, -COO- or -OCO-; R2 is a divalent aromatic group, divalent alicyclic group or divalent heterocyclic group; R3 is a single bond, 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, R4 is substituted with or not substituted with a fluorine atom; D represents an oxygen atom, a sulfur atom or -NR. d -, where R d This indicates an alkyl group having 1 to 3 carbon atoms or hydrogen atoms; a is an integer from 0 to 3, and 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 an alkyl group having 1 to 3 carbon atoms, wherein some or all of the hydrogen atoms of the 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, The liquid crystal alignment agent also satisfies at least one of the following requirements Z1 and Z2. Z1: The polymer as component (A) has thermally crosslinking groups A and thermally crosslinking groups B; Z2: The polymer, as component (A), has a thermally crosslinking group A, and the liquid crystal alignment agent further contains a compound having two or more thermally crosslinking groups B within its molecule as component (B). The thermal crosslinking group A and thermal crosslinking group B are each independently an organic group selected from carboxyl, protected carboxyl, amino, protected amino, alkoxymethylamide, hydroxymethylamide, hydroxyl, protected hydroxyl, epoxy, oxetyl, thiocyclopropane, isocyanate, and capped isocyanate. The selection is based on the criterion that thermal crosslinking group A and thermal crosslinking group B can undergo a crosslinking reaction by heat. Here, when both thermal crosslinking group A and thermal crosslinking group B are self-crosslinking groups, thermal crosslinking group A and thermal crosslinking group B may be the same as or different from each other.

3. The liquid crystal alignment agent according to claim 1, wherein, The monomer shown in formula (1) is the monomer shown in formula (1-1) below. In formula (1-1), Q1 is a hydrogen atom or a methyl group, Q2 is an alkyl group with 3 to 20 carbon atoms or a fluoroalkyl group with 1 to 20 carbon atoms, X and Y are independently hydrogen atoms, fluorine atoms, cyano groups, methyl groups, ethyl groups or trifluoromethyl groups, Z is a single bond, -O-, -COO- or -OCO-, Ar is an aromatic ring with or without substituents, and n is 1 or 2.

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, It includes the following processes: The process of forming a coating film by coating a liquid crystal alignment agent as described in any one of claims 1 to 3 onto a substrate; and 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 possesses the liquid crystal alignment film as described in claim 4.

7. A compound represented by the following formula (HQ): In formula (HQ), Q1 is a hydrogen atom or a methyl group; Q2 is an alkyl group with 3 to 20 carbon atoms or a fluoroalkyl group with 1 to 20 carbon atoms; X and Y are independently hydrogen atoms, fluorine atoms, cyano groups, methyl groups, ethyl groups, or trifluoromethyl groups, respectively; Z is a single bond, -O-, -COO-, or -OCO-; A and B independently represent pyrimidin-2,5-diyl, pyridin-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4- or 2,6-naphthylene, or phenylene groups substituted with or without fluorine atoms, chlorine atoms, cyano groups, alkoxy groups with 1 to 5 carbon atoms, or straight-chain or branched alkyl residues, wherein, The alkyl residue may or may not be substituted by one cyano group or one or more halogen atoms; n is 1 or 2.

8. A compound represented by any one of the following formulas (HQ-1) to (HQ-11): 。

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