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

Abstract

The present invention provides a liquid crystal alignment film and a liquid crystal alignment agent which are capable of stably generating a tilt angle from the vertical and obtaining high reliability. The present invention provides a liquid crystal alignment agent containing: a solvent; and a polymer obtained by using a monomer represented by formula (1) (in the formula, the definition of each substituent is as described in the description) as component (A).

Description

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

[0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film obtained therefrom, and a liquid crystal display device having the obtained liquid crystal alignment film. More specifically, the present invention relates to a liquid crystal aligning agent capable of providing a liquid crystal alignment film having good liquid crystal alignment properties, excellent pretilt angle expression ability, and high reliability, and a liquid crystal display device having excellent display quality.

[0002] In liquid crystal display devices, liquid crystal alignment films play a role in aligning liquid crystals in a specific direction. Currently, the main liquid crystal alignment films used industrially are produced by applying a polyimide-based liquid crystal alignment agent, consisting of a polyimide precursor such as polyamic acid (also known as polyamic acid), polyamic acid ester, or a polyimide solution, to a substrate and forming a film. Furthermore, if the liquid crystal is to be aligned parallel or tilted to the substrate surface, a surface stretching treatment by rubbing is further performed after film formation.

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

[0004] In recent years, a method utilizing an anisotropic photochemical reaction by irradiation with polarized ultraviolet light, etc. (photoalignment method) has been proposed as an alternative to the formation of protrusions or slits in the VA-type liquid crystal alignment control and the PSA technology. That is, it is known that the tilt direction of liquid crystal molecules when a voltage is applied can be uniformly controlled by irradiating a photoreactive, vertically aligning polyimide film with polarized ultraviolet light to impart alignment control ability and pretilt angle expression ability (see Patent Document 4).

[0005] VA-mode liquid crystal display elements are used in TVs and in-vehicle displays due to their high contrast and wide viewing angle. Liquid crystal display elements for TVs use backlights that generate a large amount of heat to achieve high brightness, while liquid crystal display elements used in in-vehicle applications, such as car navigation systems and instrument panels, are often used or left in high-temperature environments for long periods of time. Under such harsh conditions, gradual changes in the pretilt angle can lead to problems such as loss of initial display characteristics and display unevenness. Furthermore, the voltage retention and charge accumulation characteristics of the liquid crystal when driven are also affected by the liquid crystal alignment film. A low voltage retention ratio leads to a decrease in display screen contrast, while a high charge accumulation relative to the DC voltage can cause image burn-in. In particular, imparting a pretilt angle from the vertical is required to increase transmittance, but until now, no materials have been available that can stably maintain the tilt angle imparted by photoalignment.

[0006] JP-A-3-179323 JP-A-4-281427 Patent No. 4504626 Patent No. 4995267

[0007] As a result of investigations by the present inventors, it has been found that it is not possible to stably generate a tilt angle from the vertical and obtain high reliability by simply adjusting the amount of photoalignable groups. An object of the present invention is to provide a liquid crystal alignment film and a liquid crystal aligning agent that can impart a pretilt angle from the vertical and obtain high reliability.

[0008] The present inventors have found the following invention <X>: <X> A liquid crystal aligning agent containing, as component (A), a polymer obtained using a monomer represented by the following formula (1), and a solvent.

[0009]

[0010] In formula (1), R １１ represents a hydrogen atom or a methyl group; Ar represents an aromatic ring which may have a substituent; A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4-naphthylene, 2,6-naphthylene, or phenylene; A is optionally substituted with a fluorine atom, a chlorine atom, a cyano group, an alkoxy group having 1 to 5 carbon atoms, or a linear or branched alkyl residue, and the linear or branched alkyl residue is optionally substituted with one cyano group or one or more halogen atoms; R １ is a single bond, an oxygen atom, —COO— or —OCO—, and R ２ is a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group, and R ３ is a single bond, an oxygen atom, —COO— or —OCO—, and R ４ is a monovalent organic group having 3 to 40 carbon atoms and containing a linear or branched alkyl group or an alicyclic group having 1 to 40 carbon atoms, and R ４ may be substituted with a fluorine atom, and D is an oxygen atom, a sulfur atom, or —NR ｄ - (where R ｄ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), a is an integer of 0 to 3, and when a is 2 or more, a plurality of R １ and R ２ are each independently defined as above. X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms, and some or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms. The "wavy lines" between "C" and "A", and between "C" and "X" mean that either the E-form or the Z-form may be used. In this specification, the "wavy line" has the same meaning as above.

[0011] The present invention provides a liquid crystal alignment film and a liquid crystal alignment agent that can impart a pretilt angle from the vertical and have high reliability. Furthermore, the liquid crystal display device produced by the method of the present invention has excellent display characteristics.

[0012] The liquid crystal aligning agent of the present invention contains a polymer obtained using a monomer represented by the following formula (1) as the component (A), and a solvent.

[0013]

[0014] In formula (1), R １１ represents a hydrogen atom or a methyl group; Ar represents an aromatic ring which may have a substituent; A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4-naphthylene, 2,6-naphthylene, or phenylene; A is optionally substituted with a fluorine atom, a chlorine atom, a cyano group, an alkoxy group having 1 to 5 carbon atoms, or a linear or branched alkyl residue, and the linear or branched alkyl residue is optionally substituted with one cyano group or one or more halogen atoms; R １ is a single bond, an oxygen atom, —COO— or —OCO—, and R ２ is a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group, and R ３ is a single bond, an oxygen atom, —COO— or —OCO—, and R ４ is a monovalent organic group having 3 to 40 carbon atoms and containing a linear or branched alkyl group or an alicyclic group having 1 to 40 carbon atoms, and R ４ may be substituted with a fluorine atom, and D is an oxygen atom, a sulfur atom, or —NR ｄ - (where R ｄ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), a is an integer of 0 to 3, and when a is 2 or more, a plurality of R １ and R ２are each independently defined as above. X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms, and some or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms. The wavy lines between "C" and "A", and between "C" and "X" mean that either the E-form or the Z-form may be used.

[0015] The liquid crystal aligning agent of the present invention may satisfy at least one of the following requirements Z1 and Z2. Z1: The polymer (A) has a thermally crosslinkable group A and a thermally crosslinkable group B. Z2: The polymer (A) has a thermally crosslinkable group A and further contains, as a component (B), a compound having two or more thermally crosslinkable groups B in the molecule. The thermally crosslinkable group A and the thermally crosslinkable group B are each independently an organic group selected from the group consisting of a carboxy group, a protected carboxy group, an amino group, a protected amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxy group, a protected hydroxy group, an epoxy group, an oxetanyl group, a thiiranyl group, an isocyanate group, and a blocked isocyanate group, and are selected so that the thermally crosslinkable group A and the thermally crosslinkable group B undergo a crosslinking reaction by heat. Here, when the thermally crosslinkable group A and the thermally crosslinkable group B are both self-crosslinkable groups, the thermally crosslinkable group A and the thermally crosslinkable group B may be the same.

[0016] Here, "two or more in a molecule" means that the molecule contains two or more groups of the same kind, such as two or more epoxy groups, as well as two or more groups of different kinds, such as a combination of an epoxy group and a thiirane group. Preferably, "two or more in a molecule" means that the molecule contains two or more groups of the same kind.

[0017] The polymer (A) contained in the liquid crystal aligning agent of the present invention is highly sensitive to light, and therefore can exhibit alignment control ability even when irradiated with polarized ultraviolet light at a low exposure dose. Furthermore, by containing a thermally crosslinkable group A in the polymer (A) and also a thermally crosslinkable group B in the component, a crosslinking reaction involving the polymer (A) is possible even when the baking time of the liquid crystal aligning agent is short. This makes it easier for the anisotropy to remain (memory) in the liquid crystal alignment film when the photo-alignable moiety exhibits anisotropy due to a photoreaction, thereby improving the liquid crystal alignment and enabling the liquid crystal to exhibit a pretilt angle.

[0018] In addition, the group containing a photoalignable group of the monomer represented by the above formula (1), the thermally crosslinkable group A, and the thermally crosslinkable group B can all be side chains in a polymer, and therefore can be referred to as "side chains" as necessary. Each of the constituent elements of the present invention will be described in detail below.

[0019] <Component (A): Specific Polymer> [Monomer represented by formula (1)] In the present invention, in the monomer represented by formula (1) in the molecule, Ar is preferably a 1,4-phenylene group, a 1,3-phenylene group, a 4,4'-biphenylylene group, a 1,4-naphthylene group, a 2,6-naphthylene group, or the like. As for ring A, each hydrogen atom is preferably a group R ５ X and Y each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms. １ is a single bond, an oxygen atom, —COO— or —OCO—. ２ is a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group. ３ is a single bond, an oxygen atom, —COO— or —OCO—. ４ R is a monovalent organic group having 3 to 40 carbon atoms and containing a linear or branched alkyl group or an alicyclic group having 1 to 40 carbon atoms. ４ may be substituted with a fluorine atom. ５represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, and is preferably a methyl group, a methoxy group or a fluorine atom. a represents an integer of 0 to 3.

[0020] In formula (1), R ２ Examples of the divalent aromatic group include a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, a 2,3,5,6-tetrafluoro-1,4-phenylene group, and a naphthylene group. ２ Examples of the divalent alicyclic group include a trans-1,4-cyclohexylene group and a trans-trans-1,4-bicyclohexylene group. ２ Examples of the divalent heterocyclic group include a pyridine-2,6-diyl group, a pyridine-3,5-diyl group, a furan-2,5-diyl group, a piperazine-1,4-diyl group, and a piperidine-1,4-diyl group. ２ is preferably a 1,4-phenylene group, a trans-1,4-cyclohexylene group, or a trans-trans-1,4-bicyclohexylene group.

[0021] R ４Examples of the linear or branched alkyl group having 1 to 40 carbon atoms include linear or branched alkyl groups having 1 to 20 carbon atoms, and some or all of the hydrogen atoms of this alkyl group may be substituted with fluorine atoms. Examples of such alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-lauryl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, 4,4 , 4-trifluorobutyl group, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2-(perfluorobutyl)ethyl group, 2-(perfluorooctyl)ethyl group, 2-(perfluorodecyl)ethyl group, and the like.

[0022] R ４ Examples of the monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group include a cholestenyl group, a cholestanyl group, an adamantyl group, and groups represented by the following formula (Alc-1) or (Alc-2) (wherein R ７ are each a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 20 carbon atoms, some or all of the hydrogen atoms of the alkyl group having 1 to 20 carbon atoms may be substituted with fluorine atoms, and * indicates the bonding position).

[0023]

[0024] Examples of the monomer represented by the above formula (1) include, but are not limited to, structures represented by formulae (paa-1-ma1) to (paa-1-ma43). In the formula, "E" represents an E-form, and "t" represents a trans-form of the cyclohexyl group. 11 represents a hydrogen atom or a methyl group.

[0025]

[0026]

[0027]

[0028]

[0029] As the monomer represented by formula (1), one represented by the following formula (HQ) is preferred from the viewpoint of alignment stability and polymer solubility. The compound represented by the following formula (HQ) is also within the scope of the present invention. In formula (HQ), Q １ is a hydrogen atom or a methyl group, and Q ２ represents an alkyl group having 3 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms; X and Y each independently represent a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, or a trifluoromethyl group; Z is a single bond, -O-, -COO-, or -OCO-; A and B each independently represent pyrimidine-2,5-diyl, pyridine-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4- or 2,6-naphthylene, or phenylene, which is optionally substituted with a fluorine atom, a chlorine atom, a cyano group, an alkoxy group having 1 to 5 carbon atoms, or a straight-chain or branched-chain alkyl residue (which is optionally substituted with one cyano group or one or more halogen atoms); and n is 1 or 2.

[0030]

[0031] This compound can be produced, for example, by the method shown in Scheme 1 below. (Scheme 1) In Scheme 1, Q １ , Q ２ , A, B, X, Y, Z and n are defined as in the above formula (HQ).

[0032]

[0033] The compound represented by formula (HQ-a2) can be synthesized by subjecting a compound represented by formula (HQ-a1) and a compound represented by formula (HQ-r1) to a coupling reaction such as a Heck reaction in the presence of a metal complex catalyst, a ligand, and a base.

[0034] In the compound represented by formula (HQ-a1), LG is a substituent capable of being eliminated, and examples thereof include halogens such as F, Cl, Br, and I; p-toluenesulfonate group (—OSO ２ C ６ H ４ -p-CH ３ ), methanesulfonic acid ester group (—OSO ２ CH ３ ), a trifluoromethanesulfonic acid ester group (—OSO ２ CF ３ Among these, Br, I and trifluoromethanesulfonate groups are preferred from the viewpoint of reactivity.

[0035] The amount of the compound represented by formula (HQ-r1) used relative to the compound represented by formula (HQ-a1) is not particularly limited, but is preferably 1.0 equivalent to 10.0 equivalents, and more preferably 1.0 equivalent to 4.0 equivalents.

[0036] In this reaction, a metal complex catalyst is formed using an appropriate metal complex and ligand and used. Typically, a palladium complex or nickel complex is used as the metal complex, and depending on the reaction, it is preferable to use a copper catalyst as a co-catalyst. While various structures can be used as the metal complex catalyst, it is preferable to use a so-called low-valent palladium complex or nickel complex, and in particular, a zero-valent metal complex catalyst having a tertiary phosphine or tertiary phosphite as a ligand. Alternatively, a suitable precursor that can be easily converted to a zero-valent metal complex catalyst in the reaction system can be used. Furthermore, a metal complex that does not contain a tertiary phosphine or tertiary phosphite as a ligand can be mixed with a tertiary phosphine or tertiary phosphite as a ligand in the reaction system to generate a low-valent metal complex catalyst having a tertiary phosphine or tertiary phosphite as a ligand in the reaction system.

[0037] Examples of the tertiary phosphine or tertiary phosphite ligand 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 a mixture of two or more of these ligands are also suitably used.

[0038] As the metal complex catalyst, it is also preferable to use a combination of a palladium complex that does not contain a tertiary phosphine or tertiary phosphite and a metal complex that contains a tertiary phosphine or tertiary phosphite. In this case, the above-mentioned ligands may be further combined. Examples of palladium complexes that do not contain a tertiary phosphine or tertiary phosphite include bis(benzylideneacetone)palladium, tris(benzylideneacetone)dipalladium, bis(acetonitrile)dichloropalladium, bis(benzonitrile)dichloropalladium, palladium acetate, palladium chloride, and palladium-activated carbon. Examples of palladium complexes that contain a tertiary phosphine or tertiary phosphite as a ligand include (ethylene)bis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium, and bis(triphenylphosphine)dichloropalladium. The amount of these palladium complexes used may be a so-called catalytic amount, and is preferably 20 mol % or less, and particularly preferably 10 mol % or less, relative to the compound represented by Formula (HQ-a2). The copper catalyst used simultaneously as a promoter is preferably a monovalent one, such as copper(I) chloride, copper(I) bromide, copper(I) iodide, copper(I) acetate, etc.

[0039] Examples of the base that can be used include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, 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, collidine, pyrrolidine, piperidine, morpholine, and N-methylmorpholine; and sodium acetate, potassium acetate, and lithium acetate.

[0040] The amount of the base used relative to the compound represented by formula (HQ-a1) is not particularly limited, but is preferably 1.0 to 10.0 equivalents, and more preferably 1.0 to 6.0 equivalents.

[0041] Any reaction solvent can be used as long as it is stable, inert, and does not interfere with the reaction under the reaction conditions. Examples of reaction solvents include water, alcohols, amines, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et ２ O, i-Pr ２ Examples of solvents that can be used include: toluene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, dioxane, etc.; aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, 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 taking into consideration the ease of reaction, etc., and can be used alone or in combination of two or more. In some cases, the above solvents can be used as water-free solvents by using an appropriate dehydrating agent or drying agent.

[0042] The amount of solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent. When a solvent is used, the amount of solvent used may be 0.1 to 100 times by mass, preferably 1 to 10 times by mass, and more preferably 2 to 5 times by mass, relative to the amount of the compound represented by Formula (HQ-a1).

[0043] The reaction temperature can be selected preferably within the range of from -100°C or higher to the boiling point of the reaction solvent used, more preferably from -50 to 200°C, and particularly preferably from 20 to 150°C. The reaction time is 0.1 to 1000 hours, more preferably from 0.5 to 100 hours. The compound represented by formula (HQ-a2) obtained by the first method shown in Scheme 1 above is preferably purified by distillation, recrystallization, column chromatography using silica gel or the like, or the like. It is preferable to carry out recrystallization at as low a temperature as possible.

[0044] The compound represented by formula (HQ-a3) can be synthesized by reacting a compound represented by formula (HQ-a2) with a compound represented by formula (HQ-r2).

[0045] In the compound represented by formula (HQ-r2), R-Cl is any compound for synthesizing an acid chloride, such as thionyl chloride (SOCl ２ ), sulfuryl chloride (SO ２ Cl ２ ), phosphorus trichloride (PCl ３ ), phosphorus pentachloride (Cl ５ P), phosphorus oxychloride (POCl ３ ), oxalyl chloride ((COCl) ２ Among these, thionyl chloride and oxalyl chloride are preferred from the viewpoint of versatility.

[0046] The amount of the compound represented by formula (HQ-r2) used relative to the compound represented by formula (HQ-a2) is not particularly limited, but is preferably 1.0 equivalent to 3.0 equivalents, and more preferably 1.0 equivalent to 1.2 equivalents.

[0047] Any reaction solvent can be used as long as it is stable, inert, and does not interfere with the reaction under the reaction conditions. Examples of suitable reaction solvents include aprotic polar organic solvents (DMF (N,N-dimethylformamide), DMSO (dimethyl sulfoxide), DMAc (N,N-dimethylacetamide), NMP (N-methyl-2-pyrrolidone), etc.), ethers (Et ２ O (diethyl ether), i-Pr ２ Examples of solvents that can be used include: hexane (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, tetralin, 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 taking into consideration the ease of reaction, etc. In this case, the above solvents can be used alone or in combination of two or more. In some cases, a suitable dehydrating agent or drying agent can be used as a non-aqueous solvent.

[0048] The amount of solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent. When a solvent is used, the amount of solvent used may be 0.1 to 100 times by mass, preferably 1 to 10 times by mass, and more preferably 2 to 5 times by mass, relative to the amount of the compound represented by Formula (HQ-a2).

[0049] In order to allow the reaction to proceed more effectively, an appropriate base may be used. Typically, examples of the base that can be used include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate, organic bases such as sodium tert-butoxide and potassium tert-butoxide, and amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, and collidine.

[0050] To make the reaction proceed more efficiently, iodine or DMF (N,N-dimethylformamide) may be used as a catalyst.

[0051] The amount of the base or catalyst used is preferably 0.001 to 1.0 equivalent, more preferably 0.001 to 0.01 equivalent, relative to the compound represented by formula (HQ-a2).

[0052] The reaction temperature can be selected preferably within the range of from -100°C or higher to the boiling point of the reaction solvent used, more preferably from -50 to 200°C, and particularly preferably from 20 to 150°C. The reaction time is 0.1 to 1000 hours, more preferably from 0.5 to 100 hours. The compound represented by formula (HQ-a3) obtained by the method represented by the above reaction scheme is preferably purified by distillation, recrystallization, column chromatography using silica gel or the like, or the like. It is preferable to carry out recrystallization at as low a temperature as possible.

[0053] The compound represented by formula (HQ-a4) can be synthesized by condensation reaction of a compound represented by formula (HQ-a3) and a compound represented by formula (HQ-r3) in the presence of a base.

[0054] The amount of the compound represented by formula (HQ-r3) used relative to the compound represented by formula (HQ-a3) is not particularly limited, but is preferably 1.0 equivalent to 10.0 equivalents, and more preferably 1.0 equivalent to 5.0 equivalents.

[0055] In this reaction, an appropriate base is used. Typically, the base used may be an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, or cesium carbonate, an organic base such as sodium tert-butoxide or potassium tert-butoxide, or an amine such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, or collidine.

[0056] The amount of the base used is preferably 1.0 to 5.0 equivalents, more preferably 1.0 to 3.0 equivalents, relative to the compound represented by formula (HQ-a3).

[0057] Any reaction solvent can be used as long as it is stable, inert, and does not interfere with the reaction under the reaction conditions. Examples of suitable reaction solvents include aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et ２ O,i-Pr ２ Examples of solvents that can be used include: toluene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, dioxane, etc.; aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, 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 taking into consideration the ease of reaction, etc., and in this case, the above solvents can be used alone or in combination of two or more. In some cases, a suitable dehydrating agent or drying agent can be used as a non-aqueous solvent.

[0058] The amount of the solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent. When a solvent is used, the amount of the solvent used may be 0.1 to 100 times by mass, preferably 1 to 10 times by mass, and more preferably 2 to 6 times by mass, relative to the amount of the compound represented by Formula (HQ-a3).

[0059] The reaction temperature can be selected preferably within the range of from −100° C. or higher to the boiling point of the reaction solvent used, more preferably −50 to 100° C., particularly preferably 0 to 50° C. The reaction time is 0.1 to 1000 hours, more preferably 0.5 to 100 hours.

[0060] As a method for producing the compound represented by Formula (HQ-a4), in addition to the method shown in Scheme 1 above, the compound represented by Formula (HQ-a4) can also be produced by carrying out a condensation reaction using a compound represented by Formula (HQ-a2) and a compound represented by Formula (HQ-r3) in the coexistence of a condensing agent. Examples of the condensing agent include, but are not limited to, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, diisopropylcarbodiimide, 1,1'-carbonyldiimidazole, bis(2-oxo-3-oxazolinidyl)phosphinic acid chloride, di-2-pyridyl carbonate, triphenyl phosphite, dimethoxy-1,3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, and (2,3-dihydro-2-thioxo-3-benzoxazolyl)diphenyl phosphonate. The amount of the condensing agent added is preferably 1.0 to 3.0 equivalents relative to the compound represented by formula (HQ-a2).

[0061] The compound represented by formula (HQ) can be synthesized by condensation reaction of a compound represented by formula (HQ-a4) and a compound represented by formula (HQ-r4) in the presence of a base.

[0062] The amount of the compound represented by formula (HQ-r4) used relative to the compound represented by formula (HQ-a4) is not particularly limited, but is preferably 1.0 equivalent to 3.0 equivalents, and more preferably 1.0 equivalent to 2.0 equivalents.

[0063] In this reaction, an appropriate base is used. Typically, the base used may be an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, or cesium carbonate, an organic base such as sodium tert-butoxide or potassium tert-butoxide, or an amine such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, or collidine.

[0064] The amount of the base used is preferably 1.0 to 4.0 equivalents, more preferably 1.0 to 2.5 equivalents, relative to the compound represented by formula (HQ-a3).

[0065] Any reaction solvent can be used as long as it is stable, inert, and does not interfere with the reaction under the reaction conditions. Examples of suitable reaction solvents include aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et ２ O,i-Pr ２ Examples of solvents that can be used include: toluene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, dioxane, etc.; aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.); aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, 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 taking into consideration the ease of reaction, etc., and in this case, the above solvents can be used alone or in combination of two or more. In some cases, a suitable dehydrating agent or drying agent can be used as a non-aqueous solvent.

[0066] The amount of the solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent. When a solvent is used, the amount of the solvent used may be 0.1 to 100 times by mass, preferably 1 to 10 times by mass, and more preferably 2 to 6 times by mass, relative to the amount of the compound represented by Formula (HQ-a4).

[0067] The reaction temperature can be selected preferably within the range of from −100° C. or higher to the boiling point of the reaction solvent used, more preferably −50 to 100° C., particularly preferably 0 to 70° C. The reaction time is 0.1 to 1000 hours, more preferably 0.5 to 100 hours.

[0068] The compound represented by formula (HQ) obtained by the method shown in the above reaction scheme is preferably purified by distillation, recrystallization, column chromatography on silica gel, etc. Recrystallization is preferably carried out at as low a temperature as possible.

[0069] In addition to the method of Scheme 1 shown above, the compound represented by Formula (HQ) can also be produced by carrying out a condensation reaction using a compound represented by Formula (HQ-r3) and a compound represented by Formula (HQ-r4) in the presence of a condensing agent or a base, followed by a condensation reaction using a compound represented by Formula (HQ-a2) or Formula (HQ-a3) in the presence of a condensing agent or a base. The condensing agents described above can be used as the condensing agent.

[0070] [Thermal Crosslinkable Group A and Thermal Crosslinkable Group B] The thermal crosslinkable group A and the thermal crosslinkable group B are each independently an organic group selected from the group consisting of a carboxy group, a protected carboxy group, an amino group, a protected amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxy group, a protected hydroxy group, an epoxy group, an oxetanyl group, a thiiranyl group, an isocyanate group, and a blocked isocyanate group, and are selected so that the thermal crosslinkable group A and the thermal crosslinkable group B undergo a crosslinking reaction by heat, provided that the thermal crosslinkable group A and the thermal crosslinkable group B may be the same.

[0071] The protecting groups for the protected carboxy group, protected amino group, and protected hydroxy group in the thermally crosslinkable group A and the thermally crosslinkable group B are preferably protecting groups that are eliminated by heat. Examples of the protecting group for the carboxy group include acetal-based protecting groups such as a methoxymethyl group, an ethoxyethyl group, and a 2-tetrahydropyranyl group; and cyclic alcohol-based protecting groups. Examples of the protecting group for the hydroxy group include ether-based protecting groups such as a methyl group, an ethyl group, a tert-butyl group, a benzyl group, a p-methoxybenzyl group, and a trityl group; acetal-based protecting groups such as a methoxymethyl group, an ethoxyethyl group, and a 2-tetrahydropyranyl group; acyl-based protecting groups such as an acetyl group, a pivaloyl group, a benzoyl group, and a trichloroacetyl group; allyl-based protecting groups such as an allyl group and a methallyl group; carbamate-based protecting groups such as a tert-butoxycarbonyl group; and silyl ether-based protecting groups such as a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group. Examples of the amino-protecting group include carbamate-based protecting groups such as a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, a 1,1-dimethyl-2-cyanoethyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, and a 2-(trimethylsilyl)ethoxycarbonyl group; an amide-based protecting group, an imide-based protecting group, and a sulfonamide-based protecting group.

[0072] Such combinations of thermally crosslinkable groups A and B include a combination in which one is a carboxy group or a protected carboxy group and the other is an epoxy group, an oxetanyl group, a thiiranyl group, or a blocked isocyanate group, a combination in which one is a hydroxy group or a protected hydroxy group and the other is a blocked isocyanate group, a combination in which one is a phenolic hydroxy group or a protected phenolic hydroxy group and the other is an epoxy group, an oxetanyl group, or a thiiranyl group, a combination in which one is an amino group or a protected amino group and the other is a blocked isocyanate group, a combination in which both are N-alkoxymethylamide groups, etc. More preferred combinations include a carboxy group and an epoxy group, and a hydroxy group and a blocked isocyanate group.

[0073] In order to introduce such a thermally crosslinkable group A into the polymer that is the component (A), it is sufficient to copolymerize a monomer having the thermally crosslinkable group A. Furthermore, when the liquid crystal aligning agent of the present invention satisfies the requirement Z1, it is sufficient to copolymerize both a monomer having the thermally crosslinkable group A and a monomer having the thermally crosslinkable group B when producing the polymer that is the component (A).

[0074] Examples of the monomer having a thermal crosslinkable group include monomers having a carboxy group, 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;

[0075] Monomers having a hydroxy group, such as 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 ester, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone;

[0076] Monomers having a phenolic hydroxy group, such as hydroxystyrene, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)maleimide, and N-(hydroxyphenyl)maleimide;

[0077] Monomers having an amino group, such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate;

[0078] (meth)acrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide;

[0079] Monomers having an epoxy group, such as allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, α-ethylglycidyl acrylate, α-n-propylglycidyl acrylate, α-n-butylglycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl-6,7-epoxyheptyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide;

[0080] 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-phenyloxetane, 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-pentafluoro 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-(methacryloyloxymethyl)-2-methyloxetane, 3-(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,Monomers having an oxetanyl group, such as 4-tetrafluorooxetane, 3-(2-methacryloyloxyethyl)oxetane, 3-(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;

[0081] Monomers having a thiiranyl group, such as 2,3-epithiopropyl acrylate or methacrylate, and 2-, 3-, or 4-(β-epithiopropylthiomethyl)styrene, 2-, 3-, or 4-(β-epithiopropyloxymethyl)styrene, 2-, 3-, or 4-(β-epithiopropylthio)styrene, and 2-, 3-, or 4-(β-epithiopropyloxy)styrene;

[0082] Examples include monomers having a blocked isocyanate group, such as 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl acrylate, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl acrylate, 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate, and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate. Note that (meth)acrylamide refers to both acrylamide and methacrylamide.

[0083] In addition, in the present invention, when obtaining the specific copolymer, in addition to the monomer having a photoalignable group represented by the above formula (a-1-m) and the monomer having a thermal crosslinkable group A and, if necessary, a thermal crosslinkable group B, other monomers copolymerizable with these monomers can also be used in combination.

[0084] Specific examples of such other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, (meth)acrylic acid amide compounds, and monomers having a nitrogen-containing aromatic heterocyclic group and a polymerizable group.

[0085] Examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl 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-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

[0086] Examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl 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-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

[0087] Examples of the (meth)acrylic acid amide compound include acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, and N,N-diethylacrylamide.

[0088] Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, and 3-ethenyl-7-oxabicyclo[4.1.0]heptane.

[0089] Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

[0090] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0091] The nitrogen-containing aromatic heterocycle is represented by the following formulas [Na] to [Nb] (wherein Z ２ is a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms).

[0092]

[0093] Specific examples include an oxazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a 1-pyrazoline ring, an isoquinoline ring, a thiadiazole ring, a pyridazine ring, a triazine ring, a pyrazine ring, a phenanthroline ring, a quinoxaline ring, a benzothiazole ring, an oxadiazole ring, and an acridine ring. Furthermore, the carbon atom of these nitrogen-containing aromatic heterocycles may have a substituent containing a heteroatom. An example of such a substituent containing a heteroatom is a pyridine ring.

[0094] Examples of the monomer having a nitrogen-containing aromatic heterocyclic group and a polymerizable group include 2-(2-pyridylcarbonyloxy)ethyl (meth)acrylate, 2-(3-pyridylcarbonyloxy)ethyl (meth)acrylate, and 2-(4-pyridylcarbonyloxy)ethyl (meth)acrylate.

[0095] The other monomers used in the present invention may be used alone or in combination of two or more kinds.

[0096] The photoreactive moiety represented by the above formula (1) contained in the polymer, which is the component (A) of the liquid crystal aligning agent of the present invention, may be used alone or in combination of two or more kinds.

[0097] The photoreactive moiety represented by the above formula (1) is preferably contained in a proportion of 5 to 95 mol %, 5 to 60 mol %, or 5 to 40 mol % of all repeating units of the polymer that is component (A).

[0098] The moiety having a thermal crosslinkable group to be contained in the polymer of the present invention may be a single thermal crosslinkable group A, or may be a combination of two or more moieties containing a thermal crosslinkable group A and a thermal crosslinkable group B. The amount of the moiety having a thermal crosslinkable group introduced is preferably 5 to 95 mol %, 40 to 95 mol %, or 60 to 95 mol % of all repeating units of the polymer that is component (A).

[0099] The content of the structure derived from the other monomers is preferably 0 to 40 mol %, 0 to 30 mol %, or 0 to 20 mol % of all repeating units of the polymer that is component (A).

[0100] <Method for producing specific polymer> The specific polymer of component (A) contained in the liquid crystal aligning agent of the present invention is obtained by copolymerizing a monomer having a photoalignable group represented by the above formula (1), a monomer having the above thermal crosslinkable group A, and, if desired, a monomer having the above thermal crosslinkable group B. In addition, it can be copolymerized with the other monomers described above.

[0101] The method for producing the specific polymer of component (A) in the present invention is not particularly limited, and a general-purpose method used industrially can be used. Specifically, the polymer can be produced by cationic polymerization, radical polymerization, or anionic polymerization using the vinyl group of the monomer. Among these, radical polymerization is particularly preferred from the viewpoint of ease of reaction control. As the polymerization initiator for radical polymerization, known compounds such as radical polymerization initiators and reversible addition-fragmentation chain transfer (RAFT) polymerization reagents can be used.

[0102] The radical thermal polymerization initiator is a compound that generates radicals when heated to a temperature equal to or higher than its decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), and azo compounds (azobisisobutyronitrile, 2,2′-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.).

[0103] Such radical thermal polymerization initiators can be used alone or in combination of two or more.

[0104] The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by irradiation with light. Examples of such radical photopolymerization initiators include known compounds such as benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, and isopropylxanthone. These compounds may be used alone or in combination of two or more. The radical polymerization method is not particularly limited, and examples that can be used include emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, and solution polymerization.

[0105] The solvent used in the polymerization reaction of the specific polymer of component (A) is not particularly limited as long as it dissolves the resulting polymer. Specific examples include the solvents described in the section below under <Solvent>, such as N-alkyl-2-pyrrolidones, dialkylimidazolidinones, lactones, carbonates, ketones, compounds represented by formula (Sv-1) and formula (Sv-2), tetrahydrofuran, 1,4-dioxane, dimethyl sulfone, and dimethyl sulfoxide. These solvents may be used alone or in combination. Furthermore, even if a solvent does not dissolve the resulting polymer, it may be mixed with the above-mentioned solvents to the extent that the resulting polymer does not precipitate. Furthermore, since oxygen in the solvent inhibits the polymerization reaction in radical polymerization, it is preferable to use an organic solvent that has been degassed to the greatest extent possible.

[0106] The polymerization temperature during radical polymerization can be selected from any temperature between 30 and 150°C, but is preferably in the range of 50 to 100°C. Furthermore, the reaction can be carried out at any concentration, but the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction can be carried out at a high concentration initially, and then an organic solvent can be added. In the above-mentioned radical polymerization reaction, if the ratio of radical polymerization initiator to monomer is high, the molecular weight of the resulting polymer will be small; if the ratio is low, the molecular weight of the resulting polymer will be large. Therefore, the ratio of radical initiator to monomer to be polymerized is preferably 0.1 to 10 mol%. Furthermore, various monomer components, solvents, initiators, etc. can also be added during polymerization.

[0107] [Polymer Recovery] When recovering the polymer produced from the reaction solution obtained by the above-mentioned reaction, the reaction solution may be poured into a poor solvent to precipitate the polymer. Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer precipitated by pouring into the poor solvent can be recovered by filtration and then dried at room temperature or by heating under atmospheric or reduced pressure. Furthermore, the polymer precipitated and recovered can be redissolved in an organic solvent and reprecipitated and recovered two to ten times to reduce the amount of impurities in the polymer. Examples of poor solvents include alcohols, ketones, and hydrocarbons. Using three or more poor solvents selected from these solvents is preferred because it further increases the efficiency of purification.

[0108] The molecular weight of the specific polymer of component (A) is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000, in terms of weight average molecular weight measured by GPC (Gel Permeation Chromatography), taking into consideration the strength of the resulting coating film, workability during coating film formation, and uniformity of the coating film.

[0109] <Component (B)> When the liquid crystal aligning agent used in the present invention satisfies requirement Z2, it contains a crosslinking agent as component (B). Examples of component (B) include a crosslinking agent having two or more thermal crosslinkable groups B.

[0110] Examples of the crosslinking agent as component (B) include low molecular weight compounds such as epoxy compounds, compounds having two or more amino groups, methylol compounds, isocyanate compounds, phenoplast compounds, and blocked isocyanate compounds, as well as polymers such as polymers of N-alkoxymethylacrylamide, polymers of compounds having an epoxy group, and polymers of compounds having an isocyanate group.

[0111] Specific examples of the 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, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane.

[0112] Examples of compounds having two or more amino groups include diamines such as alicyclic diamines, aromatic diamines, aromatic-aliphatic diamines, and aliphatic diamines.

[0113] Examples of the alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, and isophoronediamine.

[0114] 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.

[0115] Examples of aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 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-naphthylmethanamine, 6-amino-3-naphthylmethanamine, 2-(6-amino-2-naphthyl)ethylamine, 2-(6-amino-3-naphthyl)ethylamine, and the like.

[0116] 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.

[0117] Specific examples of the methylol compound include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

[0118] Specific examples of alkoxymethylated glycolurils include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins (high condensation type, trade names: Beckamin (registered trademark) J-300S, P-955, N) manufactured by DIC Corporation.

[0119] Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Commercially available products include those manufactured by Allnex (trade name: Cymel (registered trademark) 1123) and those manufactured by Sanwa Chemical Co., Ltd. (trade names: Nikalac (registered trademark) BX-4000, BX-37, BL-60, and BX-55H).

[0120] Specific examples of alkoxymethylated melamine include hexamethoxymethyl melamine, etc. Commercially available products include methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, and 350) and butoxymethyl type melamine compounds (trade names: Mycoat (registered trademark) 506 and 508) manufactured by Allnex Corporation, and methoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, and MX-035) and butoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MX-45, MX-410, and MX-302) manufactured by Sanwa Chemical Co., Ltd.

[0121] Furthermore, compounds obtained by condensing melamine compounds, urea compounds, glycoluril compounds, and benzoguanamine compounds in which the hydrogen atoms of the amino groups have been substituted with methylol groups or alkoxymethyl groups may also be used. Examples include high molecular weight compounds produced from melamine compounds and benzoguanamine compounds described in U.S. Patent No. 6,323,310. Commercially available melamine compounds include Cymel (registered trademark) 303 (manufactured by Allnex), and commercially available benzoguanamine compounds include Cymel (registered trademark) 1123 (manufactured by Allnex).

[0122] Specific examples of the isocyanate compound include VESTANAT B1358 / 100 and VESTAGON BF 1540 (both are isocyanurate-modified polyisocyanates, manufactured by Evonik Japan Co., Ltd.), Takenate (registered trademark) B-882N and Takenate B-7075 (both are isocyanurate-modified polyisocyanates, manufactured by Mitsui Chemicals, Inc.), and the like.

[0123] Specific examples of the phenoplast compound include the following compounds, but the phenoplast compound is not limited to the following compound examples.

[0124]

[0125] Specific examples of the compound having two or more hydroxyalkylamide groups at the molecular terminal include the following compounds and Primid (registered trademark) QM-1260 and SF-4510 (all manufactured by EMS-CHEMIE).

[0126]

[0127] Examples of blocked isocyanate compounds include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, and Millionate MS-50 (all manufactured by Tosoh Corporation), and Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, and B-882N (all manufactured by Mitsui Chemicals, Inc.).

[0128] Furthermore, examples of the above-mentioned N-alkoxymethylacrylamide polymers include polymers produced using acrylamide compounds or methacrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide.

[0129] Specific examples of such polymers include poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate, etc. The weight-average molecular weight of such polymers is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

[0130] Examples of polymers of compounds having an epoxy group include polymers produced using compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate.

[0131] Specific examples of such polymers include poly(3,4-epoxycyclohexylmethyl methacrylate), poly(glycidyl methacrylate), a copolymer of glycidyl methacrylate and methyl methacrylate, a copolymer of 3,4-epoxycyclohexylmethyl methacrylate and methyl methacrylate, a copolymer of glycidyl methacrylate and styrene, etc. The weight-average molecular weight of such polymers is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

[0132] Examples of the polymer of the compound having an isocyanate group include a polymer produced using a compound having an isocyanate group, such as 2-isocyanatoethyl methacrylate (Karenz MOI [registered trademark], manufactured by Showa Denko K.K.) or 2-isocyanatoethyl acrylate (Karenz AOI [registered trademark], manufactured by Showa Denko K.K.), or a compound having a blocked isocyanate group, such as 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (Karenz MOI-BM [registered trademark], manufactured by Showa Denko K.K.) or 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP [registered trademark], manufactured by Showa Denko K.K.).

[0133] Specific examples of such polymers include poly(2-isocyanatoethyl acrylate), poly(2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate), a copolymer of 2-isocyanatoethyl methacrylate and styrene, and a copolymer of 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate and methyl methacrylate. The weight-average molecular weight of such polymers is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

[0134] These crosslinking agents may be used alone or in combination of two or more.

[0135] When the liquid crystal aligning agent used in the present invention contains the crosslinking agent of the component (B), the content thereof is preferably 1 to 100 parts by mass, more preferably 1 to 80 parts by mass, based on 100 parts by mass of the component (A).

[0136] <Component (C)> The liquid crystal aligning agent of the present invention may contain, as component (C), a polymer selected from a polyamic acid (P') and its imidized polymer (P). The polyamic acid (P') can be obtained by a polymerization reaction of a diamine component with a tetracarboxylic acid component containing a tetracarboxylic dianhydride.

[0137] (Diamine) As the diamine component used in the production of the polyamic acid (P'), various diamines can be used depending on the purpose. The diamines used in the production of the polyamic acid (P') may be used alone or in combination of two or more. Preferred specific examples of the diamines used in the production of the polyamic acid (P') (hereinafter also referred to as diamine (p)) include the following diamines:

[0138] Aromatic diamines (d) represented by "A-X-J" (details will be 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, Phenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 2,5-di Aminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenyl)ethane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4-amino-2-methylphenyloxy)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis (3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, 3-[2-[2-(4-aminophenoxy)ethoxy]ethoxy]benzenamine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 4,4'-bis(4-amino phenoxy)diphenyl, 4,4'-bis(4-aminophenoxy)diphenyl ether, 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, 1,2-bis(6-amino-2-naphthyloxy)ethane, 1,2-bis(6-amino-2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 4'-[2-(4-aminophenoxy)ethoxy]-[1,1'-biphenyl]-4-amine, 1,4-bis[2-(4-aminophenyl)ethyl]butanedioate, 1,6-bi bis[2-(4-aminophenyl)ethyl]hexanedioate, 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate; 4,4'-diaminoazobenzene, diaminotolan, 4,4'-diaminochalcone, or [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, or [4-[(E)-3-[[5-amino-2-[4-amino-2-[[(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,diamines having a photoalignment group, such as aromatic diamines having a cinnamate structure in the side chain, typified by 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone and 2-(4-(2-hydroxy-2-methylpropanoyl)phenoxy)ethyl 3,5-diaminobenzoate; diamines having a photopolymerizable group at the end, such as 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4-diamino-N,N-diallylaniline; benzoins or diamines typified by 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone and 2-(4-(2-hydroxy-2-methylpropanoyl)phenoxy)ethyl 3,5-diaminobenzoate; or their alkyl ethers, benzil ketals, acetophenones, acylphosphine oxides, benzophenones, or aminobenzophenones, or other diamines having a group in the molecule that exhibits radical polymerization initiator function; diamines having an amide bond such as 4,4'-diaminobenzanilide, and diamines having a urea bond such as 1,3-bis(4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, and 1,3-bis(4-aminophenethyl)urea; 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline , bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-( 4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(3-amino-4-methylphenyl)propane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-Diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene; 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl phenyl-3,6-diaminocarbazole, N-[3-(1H-imidazol-1-yl)propyl]-3,5-diaminobenzamide, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl]-benzenamine, 1,4-bis(p-aminobenzyl)piperazine, 4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)dianiline, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, compounds of the following formula (z- 1) Diamines represented by formulas (z-5), 2,5-bis(4-aminophenyl)pyrrole, 4,4'-(1-methyl-1H-pyrrole-2,5-diyl)bis[benzenamine], 1,4-bis-(4-aminophenyl)-piperazine, 2-N-(4-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 heterocycle-containing diamines such as benzophenone, 5-(1H-benzimidazol-2-yl)benzene-1,3-diamine, or 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)-1,4-benzenediamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,Diamines having at least one nitrogen-containing structure selected from the group consisting of a nitrogen-containing heterocycle, a secondary amino group, and a tertiary amino group, typified by diamines having a diphenylamine structure such as 4-benzenediamine (provided that the molecule does not contain an amino group bonded to a protecting group that is eliminated by heating and replaced with a hydrogen atom); 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 1,2-bis(4- diamines having a carboxy group such as 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 1,2-bis(4-aminophenyl)ethane-3,3'-dicarboxylic acid, and 4,4'-diaminodiphenylether-3,3'-dicarboxylic acid; ; 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diamino-3,3'-dihydroxybiphenyl; 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine; N1,N 6-Bis(2-tert-butoxycarbonylamino-4-aminophenyl)adipamide, 4-amino-N-(2-tert-butoxycarbonylamino-4-aminophenyl)benzamide, carbamic acid, N-[(2,5-diaminophenyl)methyl]-, 1,1-dimethylethyl ester, carbamic acid, N-[3-(2,5-diaminophenyl)propyl]-, 1,1-dimethylethyl ester, carbamic acid, N,N-[(2,5-diamino-1,3-phenylene)di-3,1-propanediyl]bis-, C,C-bis(1,1-dimethylethyl) ester, N-tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine, benzoic acid, 4-amino-2-tert-butoxycarbonylamino-,1,1'-[(1,1,3,3-tetramethyl-1,3-disiloxanediyl)di-4,1-butanediyl] ester, carbamic acid, N-[2-(4-aminophenyl)ethyl]-N-[[[2-(4-aminophenyl)ethyl]amino]carbonyl]-,1,1-dimethylethyl ester, carbamic acid, N-(4-aminophenyl)-N-[[1-(4-aminophenyl)-4-piperidinyl]methyl]-,1,1-dimethylethyl ester, and the like. a diamine having a protecting group (a protecting group between 1 and 2 carbon atoms), a long chain alkyl group having 12 to 20 carbon atoms, represented by 1-dodecanoxy-2,4-diaminobenzene, 1-tetradecanoxy-2,4-diaminobenzene, 1-pentadecanoxy-2,4-diaminobenzene, 1-hexadecanoxy-2,4-diaminobenzene, 1-octadecanoxy-2,4-diaminobenzene, 1-dodecanoxy-2,5-diaminobenzene, 1-tetradecanoxy-2,5-diaminobenzene, 1-pentadecanoxy-2,5-diaminobenzene, 1-hexadecanoxy-2,5-diaminobenzene, and 1-octadecanoxy-2,5-diaminobenzene; Aromatic diamines (TN) having an alkyl group; diamines having a siloxane bond such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and 1,3-bis[3-(p-aminophenylcarbamoyl)propyl]tetramethyldisiloxane; metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and diamines in which two amino groups are bonded to a group represented by any one of formulas (Y-1) to (Y-167) described in WO 2018 / 117239, etc.

[0139]

[0140] In the aromatic diamine (d) represented by "A-X-J," A represents a monovalent group in which two primary amino groups are bonded to an aromatic group. Specific examples of the aromatic group include a benzene ring, a naphthalene ring, and a biphenyl structure. X represents a single bond, -(CH ２ ) ａ -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH ３ )-, -NH-, -O-, -COO-, -OCO- or -(A ０ ) ｍ０ -((CH ２ ) ａ１ -A １ ) ｍ１ - (a1 is an integer from 1 to 15, A ０、 A １ represents an oxygen atom or —COO—, m0 is an integer of 0 or 1, and m1 is an integer of 1 to 2. When m1 is 2, a plurality of a1 and A １ are each independently defined as above. ) J represents a monovalent organic group having at least one group selected from the group consisting of alicyclic hydrocarbon groups having 4 to 40 carbon atoms and aromatic hydrocarbon groups having 6 to 40 carbon atoms. However, at least one hydrogen atom of the alicyclic hydrocarbon group and aromatic hydrocarbon group is substituted with a substituent (v) which is any one of a halogen atom, a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, and an alkenyl group having 3 to 10 carbon atoms. Furthermore, any carbon-carbon single bond in these substituents (v) (excluding halogen atoms) may be interrupted by -O-. In addition to the above alicyclic hydrocarbon groups and aromatic hydrocarbon groups, J may further have at least one group selected from the group consisting of alicyclic hydrocarbon groups and aromatic hydrocarbon groups that are unsubstituted or substituted with a substituent other than the above substituent (v).

[0141] Examples of halogen atom-containing alkyl groups include halogen atom-containing alkyl groups having 1 to 10 carbon atoms. Examples of halogen atom-containing alkoxy groups include halogen atom-containing alkoxy groups having 1 to 10 carbon atoms.

[0142] Examples of the alicyclic hydrocarbon group of J include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cyclodecane ring, and a steroid skeleton (for example, a cholestanyl group, a cholesteryl group, a lanostaniyl group, etc.), and examples of the aromatic hydrocarbon group include a benzene ring and a naphthalene ring. When J has at least one of a cyclohexane ring and a benzene ring, the group "-X-J" can include, for example, the following structure (S1), and more preferred structures are those represented by the following formulae (S1-1) to (S1-5) (wherein, X １ , R １ , * is X in formula (S1) １ , R １ , * is synonymous with *.

[0143]

[0144] In the formula, X １ is a single bond, -(CH ２ ) ａ -(a is an integer of 1 to 15), -CONH-, -CO-N(CH ３ )-, -NH-, -O-, -COO-, or -(A ０ ) ｍ０ -((CH ２ ) ａ１ -A １ ) ｍ１ - (a1 is an integer from 1 to 15, A ０、 A １ represents an oxygen atom or —COO—, m0 is an integer of 0 or 1, and m1 is an integer of 1 to 2. When m1 is 2, a plurality of a1 and A １ are each independently defined as above. * represents a bonding position. １ represents a divalent cyclic group selected from a phenylene group and a cyclohexylene group. Any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. m is an integer of 1 to 4. When m is 2 or more, multiple X １ , G １ Each independently has the definition above. １represents a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkoxyalkyl group having 3 to 10 carbon atoms.

[0145]

[0146] Specific examples of the aromatic diamine (d) include diamines represented by the following formulas (d-1) and (d-2): More preferred specific examples include diamines represented by formulas (d-1) to (d-2) in which the group "-X-J" is either the above structure (S1) or any of the above formulas (S1-1) to (S1-5), as well as diamines having a steroid skeleton such as cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, and 3,6-bis(4-aminobenzoyloxy)cholestane.

[0147]

[0148] X and J have the same meanings as X and J in the aromatic diamine (d), including preferred embodiments. In the formula (d-2), the two Xs and Js may be the same or different.

[0149] When the aromatic diamine (d) is used as the diamine (p), it preferably accounts for 5 to 95 mol %, more preferably 10 to 90 mol %, of the total diamine components used to produce the polyamic acid (P').

[0150] (Tetracarboxylic acid dianhydride) The tetracarboxylic acid dianhydride that can be used in the synthesis of the polyamic acid (P') can be at least one compound selected from the group consisting of acyclic aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and aromatic tetracarboxylic acid dianhydrides. Among these, it is more preferable to include a tetracarboxylic acid dianhydride having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure, and it is even more preferable to include a tetracarboxylic acid dianhydride having at least one partial structure selected from the group consisting of a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure.

[0151] The tetracarboxylic acid component that can be used in the synthesis of the polyamic acid (P') preferably contains the following tetracarboxylic acid dianhydrides (hereinafter, these may also be collectively referred to as specific tetracarboxylic acid dianhydrides): The above tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

[0152] acyclic aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic acid dianhydride; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3',4,4'-di ... 2,3,5-Tricarboxycyclopentylacetic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)- alicyclic tetracarboxylic acid dianhydrides such as 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, and 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride;Pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 4,4'-bis(3, Aromatic tetracarboxylic acid dianhydrides such as 4-dicarboxyphenoxy)diphenylpropane dianhydride, ethylene glycol bisanhydrotrimellitate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-(1,4-phenylenedioxy)bis(phthalic anhydride), and 4,4'-(1,4-phenylenedimethylene)bis(phthalic anhydride); and also tetracarboxylic acid dianhydrides such as those described in JP 2010-97188 A.

[0153] Preferred examples of the specific tetracarboxylic acid derivatives include 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 5-(2, 5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, pyromellitic dianhydride, 3,3',4,4 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyltetracarboxylic dianhydride.

[0154] The proportion of the specific tetracarboxylic dianhydride used is preferably 10 mol % or more, more preferably 20 mol % or more, and even more preferably 50 mol % or more, based on 1 mol of the total tetracarboxylic acid components used.

[0155] (Synthesis of Polyamic Acid) Polyamic acid is synthesized by reacting a diamine component containing the diamine described above with a tetracarboxylic acid component containing the tetracarboxylic acid dianhydride or a derivative thereof in an organic solvent. The ratio of tetracarboxylic acid dianhydride and diamine used in the polyamic acid synthesis reaction is preferably such that 0.5 to 2 equivalents of acid anhydride groups in the tetracarboxylic acid dianhydride are present per equivalent of amino groups in the diamine, more preferably 0.8 to 1.2 equivalents. As with conventional polycondensation reactions, the closer the equivalent of the acid anhydride groups in the tetracarboxylic acid dianhydride is to 1 equivalent, the higher the molecular weight of the resulting polyamic acid. The reaction temperature in the polyamic acid synthesis reaction is preferably −20 to 150°C, more preferably 0 to 100°C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours. The polyamic acid synthesis reaction can be carried out at any concentration, but is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction may be carried out at a high concentration in the initial stage, and then additional solvent may be added.

[0156] Specific examples of the organic solvent include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. When the polymer has high solubility in the solvent, 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, and diethylene glycol monoethyl ether can be used.

[0157] <End-capping Agent> When synthesizing the polyamic acid of the present invention, an end-capping polymer may be synthesized using a tetracarboxylic acid component containing a tetracarboxylic dianhydride or a derivative thereof, a diamine component containing the above-mentioned diamine, and an appropriate end-capping agent. The end-capping polymer has the effect of improving the film hardness of the alignment film obtained by coating and improving the adhesion properties between the sealing agent and the alignment film. Examples of the terminals of the polyamic acid of the present invention include amino groups, carboxy groups, acid anhydride groups, and groups derived from the end-capping agents described below. The amino groups, carboxy groups, and acid anhydride groups can be obtained by a conventional condensation reaction or by blocking the terminals with the following end-capping agents.

[0158] Examples of the end-capping agent include acid anhydrides such as acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilyl)propyl-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, and 4-ethynylphthalic anhydride; dicarbonate diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, and nicotinic acid chloride; and aniline. Examples of the amino acid ester include monoamine compounds such as 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; and isocyanates having an unsaturated bond such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, or 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate.

[0159] The proportion of the end-capping agent used is preferably 0.01 to 20 parts by mole, and more preferably 0.01 to 10 parts by mole, per 100 parts by mole of the total of the diamine components used.

[0160] The polyamic acid preferably has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the number average molecular weight (Mn) in terms of polystyrene measured by GPC, is preferably 15 or less, more preferably 10 or less. Having the molecular weight in this range ensures good alignment in liquid crystal display elements.

[0161] <Imidization of Polyamic Acid> Methods for imidizing polyamic acid include thermal imidization, in which a solution of polyamic acid is heated as is, and catalytic imidization, in which a catalyst is added to a solution of polyamic acid. When thermally imidizing polyamic acid in a solution, the temperature is 100°C to 400°C, preferably 120°C to 250°C, and it is preferable to carry out the thermal imidization while removing water produced by the imidization reaction from the system.

[0162] Chemical (catalytic) imidization of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a solution of polyamic acid and stirring the system at a temperature of −20 to 250° C., preferably 0 to 180° C. The amount of the basic catalyst is 0.5 to 30 times, preferably 1.5 to 20 times by mole, the amount of the amic acid groups in the polyamic acid, and the amount of the acid anhydride is 1 to 50 times, preferably 2 to 30 times by mole, the amount of the amic acid groups in the polyamic acid.

[0163] Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and 1-ethylpiperidine, with pyridine and 1-ethylpiperidine being preferred because they have an appropriate level of basicity for promoting the reaction. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, with acetic anhydride being preferred because it facilitates purification after completion of the reaction. The imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0164] In the polyimide resin used in the present invention, the dehydration ring closure rate (imidization rate) of the amic acid group does not necessarily need to be 100% and can be adjusted as desired depending on the application and purpose. It is particularly preferably 50% or more.

[0165] <Polymer Recovery> When recovering and using the polymer component from the reaction solution of polyamic acid and polyimide, the reaction solution may be precipitated by pouring it into a poor solvent. Examples of poor solvents used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated by pouring it into the poor solvent can be recovered by filtration and then dried at room temperature or by heating under atmospheric or reduced pressure. Furthermore, the precipitated polymer can be redissolved in an organic solvent, reprecipitated, and recovered (reprecipitation recovery step) two to ten times, thereby reducing the amount of impurities in the polymer. In this case, it is preferable to use three or more poor solvents, such as alcohols, ketones, and hydrocarbons, as the poor solvent, as this further increases the efficiency of purification.

[0166] The organic solvent used to dissolve the resin component in the reprecipitation and recovery step is not particularly limited. 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, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, and 4-hydroxy-4-methyl-2-pentanone. Two or more of these solvents may be mixed and used.

[0167] In the liquid crystal aligning agent of the present invention, when a polymer of component (C) is used, the content ratio of the polymer of component (A) to the polymer of component (C) is preferably a mass ratio of component (A):component (C) of 1:99 to 90:10, more preferably 5:95 to 70:30, and even more preferably 10:90 to 50:50.

[0168] [Preparation of Liquid Crystal Alignment Agent] The liquid crystal aligning agent used in the present invention is preferably prepared as a coating liquid suitable for forming a liquid crystal alignment film. That is, the liquid crystal aligning agent of the present invention is preferably prepared as a solution in which a resin component for forming a resin coating is dissolved in an organic solvent. Here, the resin components are the polymer (component (A)) already described, the crosslinking agent (component (B)) if necessary, and the polyamic acid (P') (component (C)) if necessary. In this case, the total content of the component (A), the crosslinking agent (component (B)), and the polyamic acid (P') (component (C)) is preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, even more preferably 1 to 15% by mass, and particularly preferably 1 to 10% by mass, based on the total amount of the liquid crystal aligning agent.

[0169] <Solvent> The solvent contained in the liquid crystal aligning agent used in the present invention is not particularly limited as long as it is a solvent that dissolves the (A) component, and optionally the (B) component, and optionally the (C) component. The solvent contained in the liquid crystal aligning agent may be one type, or two or more types may be mixed and used. Furthermore, even if the solvent does not dissolve the (A) component or the (B) component, it can be used in combination with a solvent that dissolves the (A) component or the (B) component. In this case, it is preferable that the surface energy of the solvent that does not dissolve the (A) component or the (B) component is lower than that of the solvent that dissolves the (A) component or the (B) component, because this improves the coatability of the liquid crystal aligning agent to the substrate.

[0170] Specific examples include water, N-alkyl-2-pyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylcaprolactam, tetramethylurea, dialkylimidazolidinones such as 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide and 1,3-dimethyl-2-imidazolidinone, lactones such as γ-butyrolactone, γ-valerolactone and δ-valerolactone, carbonates such as ethylene carbonate and propylene carbonate, methanol, ethanol and propanol. ketones such as methyl ketone, isopropanol, 3-methyl-3-methoxybutanol, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, isoamyl methyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, and 4-hydroxy-4-methyl-2-pentanone; compounds represented by the following formula (Sv-1) and the following formula (Sv-2); 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, isoamyl butyrate, diisobutyl carbinol, and diisopentyl ether.

[0171]

[0172] In formulas (Sv-1) to (Sv-2), Y １ and Y ２ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and X １ is an oxygen atom or —COO—, and X ２ is a single bond or a carbonyl group, and R １ is an alkylene group having 2 to 4 carbon atoms. １ is an integer from 1 to 3. １ When is 2 or 3, multiple R １ may be the same or different. １ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Y ３ and Y ４are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

[0173] In formula (Sv-1), Y １ and Y ２ Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include a monovalent chain hydrocarbon group having 1 to 6 carbon atoms, a monovalent alicyclic hydrocarbon group having 1 to 6 carbon atoms, and a monovalent aromatic hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent chain hydrocarbon group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms. R １ The alkylene group may be linear or branched.

[0174] In formula (Sv-2), Z １ Examples of the divalent hydrocarbon group having 1 to 6 carbon atoms include an alkylene group having 1 to 6 carbon atoms. ３ and Y ４ Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include a monovalent chain hydrocarbon group having 1 to 6 carbon atoms, a monovalent alicyclic hydrocarbon group having 1 to 6 carbon atoms, and a monovalent aromatic hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent chain hydrocarbon group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms.

[0175] Specific examples of the solvent represented by formula (Sv-1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl 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, and 3-ethoxybutyl acetate; Specific examples of the solvent represented by (Sv-2) include methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, and butyl 3-methoxypropionate.

[0176] The solvent preferably has a boiling point of 80 to 200° C. More preferably, it is 80 to 180° C. Preferred solvents include N,N-dimethylformamide, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, propanol, isopropanol, 3-methyl-3-methoxybutanol, ethyl amyl ketone, methyl ethyl ketone, isoamyl methyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, 4-hydroxy-4-methyl-2-pentanone, 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, isoamyl butyrate, diisobutylcarbinol, diisopentyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, and ethylene glycol-i-propyl 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. A boiling point in this range is particularly preferred when a liquid crystal alignment agent containing the solvent is applied to a plastic substrate, which will be described later.

[0177] <Other Components> The liquid crystal aligning agent used in the present invention may contain other components in addition to the above-mentioned component (A), if necessary the component (B), and if necessary the component (C). Examples of such other components include, but are not limited to, a crosslinking catalyst, a compound that improves the film thickness uniformity and surface smoothness when the liquid crystal aligning agent is applied, and a compound that improves the adhesion between the liquid crystal alignment film and the substrate.

[0178] <Crosslinking Catalyst> A crosslinking catalyst may be added to the liquid crystal aligning agent used in the present invention for the purpose of promoting the reaction between the thermally crosslinkable group A and the thermally crosslinkable group B. Examples of such a crosslinking catalyst include sulfonic acids such as 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, and dodecylbenzenesulfonic acid, as well as hydrates and salts thereof. Examples of the compound that generates an acid when heated include bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylene tris(methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, and N-ethyl-p-toluenesulfonamide.

[0179] [Compounds for Improving Film Thickness Uniformity and Surface Smoothness] Examples of compounds for improving film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples include Eftop (registered trademark) 301, EF303, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F171, F173, and R-30 (manufactured by DIC Corporation), Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited), Asahiguard (registered trademark) AG710 (manufactured by AGC), and Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Seimi Chemical Co., Ltd.). The proportion of these surfactants used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the polymer composition.

[0180] [Compound for improving adhesion between liquid crystal alignment film and substrate] Specific examples of the compound for improving adhesion between a liquid crystal alignment film and a substrate include the following functional silane-containing compounds. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-3-triethoxysilylpropyltriethylene Examples of such compounds include amino-based silane-containing compounds such as N-trimethoxysilylpropyltriethylenetetramine, N-3-trimethoxysilylpropyltriethylenetetramine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane. When a compound that improves adhesion to a substrate is used, the amount used is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the resin component contained in the polymer composition.

[0181] In some embodiments, a photosensitizer can be used as an additive to improve the photoreactivity of the photoalignment group. Specific examples include aromatic 2-hydroxyketones (benzophenones), coumarins, ketocoumarins, carbonylbiscoumarins, acetophenones, anthraquinones, xanthones, thioxanthones, and acetophenone ketals.

[0182] <Liquid Crystal Alignment Film and Liquid Crystal Display Element> The liquid crystal alignment agent of the present invention can be applied to a substrate, baked, and then subjected to alignment treatment such as rubbing or light irradiation to form a liquid crystal alignment film, or in some applications such as vertical alignment, no alignment treatment is required. Examples of substrates that can be used include glass such as float glass and soda glass; transparent substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polypropylene, polystyrene, polyethersulfone, polycarbonate, poly(alicyclic olefin), polyvinyl chloride, polyvinylidene chloride, polyetheretherketone (PEEK) resin film, polysulfone (PSF), polyethersulfone (PES), polyamide, polyimide, acrylic, and triacetylcellulose. Examples of transparent conductive films provided on one side of the substrate include tin oxide (SnO ２ NESA membrane (registered trademark of PPG, USA) consisting of indium oxide-tin oxide (In ２ O ３ -SnO ２ ) or the like can be used.

[0183] <Coating Film Forming Step> The method for applying the liquid crystal aligning agent of the present invention is not particularly limited, and examples thereof include screen printing, flexographic printing, offset printing, inkjet printing, dip coating, roll coating, slit coating, spin coating, etc., which may be used depending on the purpose. After applying the liquid crystal aligning agent to a substrate by these methods, the solvent is evaporated by a heating means such as a hot plate to form a coating film.

[0184] Baking after application of the liquid crystal alignment agent can be carried out at any temperature between 40 and 300°C, preferably between 40 and 250°C, and more preferably between 40 and 230°C. The thickness of the coating film formed on the substrate is preferably between 5 and 1,000 nm, and more preferably between 10 and 500 nm or between 10 and 300 nm. This baking can be carried out using a hot plate, a hot air circulating oven, an infrared oven, or the like. For the rubbing treatment, a rayon cloth, a nylon cloth, a cotton cloth, or the like can be used.

[0185] <Light Irradiation Step> In an embodiment, an alignment treatment by light irradiation may be performed, and may include, for example, a step of applying the liquid crystal alignment agent described above onto a substrate to form a coating film, and a step of irradiating the coating film with light in a state where the coating film is not in contact with the liquid crystal layer or in a state where the coating film is in contact with the liquid crystal layer.

[0186] Examples of light to be irradiated in the alignment treatment by light irradiation include ultraviolet light containing light with a wavelength of 150 to 800 nm and visible light. Of these, ultraviolet light containing light with a wavelength of 300 to 400 nm is preferred. The irradiated light may be polarized or unpolarized. As the polarized light, it is preferable to use light containing linearly polarized light.

[0187] When the light used is polarized light, the light may be irradiated from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these. When irradiating with unpolarized light, the light is preferably irradiated from an oblique direction relative to the substrate surface. The light irradiation dose is 0.1 mJ / cm. ２ 1,000mJ / cm or more ２ It is preferable that the dose is less than 1 to 500 mJ / cm ２ More preferably, it is 2 to 200 mJ / cm ２ It is more preferable to set the following.

[0188] <Liquid Crystal Display Element> The liquid crystal display element of the present invention is a vertical alignment type liquid crystal display element having a liquid crystal cell including two substrates arranged facing each other, a liquid crystal layer provided between the substrates, and a liquid crystal alignment film provided between the substrates and the liquid crystal layer and formed using the liquid crystal aligning agent of the present invention. Specifically, the liquid crystal display element is a vertical alignment type liquid crystal display element having a liquid crystal cell fabricated by applying the liquid crystal aligning agent of the present invention to two substrates and baking the substrates to form a liquid crystal alignment film, then arranging the two substrates so that the liquid crystal alignment film faces the substrates, sandwiching a liquid crystal layer composed of liquid crystal between the two substrates, and irradiating the liquid crystal layer with ultraviolet light. In this way, by using the liquid crystal alignment film formed using the liquid crystal aligning 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, resulting in a liquid crystal display element with small liquid crystal residual DC and less susceptible to image sticking.

[0189] The substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate, but is typically a substrate on which a transparent electrode for driving liquid crystal is formed. Specific examples include the same substrates as those described above for the liquid crystal alignment film. The liquid crystal display element of the present invention may use a substrate provided with a conventional electrode pattern or protrusion pattern, but by having a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention, it can operate even if one substrate has a line / slit electrode pattern of 1 to 10 μm formed thereon and the opposing substrate has a structure in which no slit pattern or protrusion pattern is formed thereon. This simplifies the process of manufacturing the element and allows for high transmittance to be obtained.

[0190] Furthermore, in a highly functional element such as a TFT type element, an element such as a transistor is formed between an electrode for driving the liquid crystal and a substrate.

[0191] In the case of a transmissive liquid crystal display element, the above-mentioned substrates are generally used, but in the case of a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used as the substrate on only one side. In this case, a light-reflecting material such as aluminum can be used for the electrodes formed on the substrate.

[0192] The liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention onto the substrate and then baking it, as described above in detail.

[0193] 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, dicyanobenzene-based liquid crystals, pyridazine-based liquid crystals, Schiff base-based liquid crystals, azoxy-based liquid crystals, biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, and terphenyl-based liquid crystals can be used. It is also preferable to use an alkenyl-based liquid crystal in combination. Conventional known alkenyl-based liquid crystals can be used as such alkenyl-based liquid crystals. Examples of such alkenyl-based liquid crystals include, but are not limited to, compounds represented by the following formula:

[0194]

[0195] 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 vertical alignment mode. For example, liquid crystal compositions having negative dielectric anisotropy, such as MLC-6608 and MLC-6609 manufactured by Merck & Co., Ltd., can be used. Furthermore, liquid crystal compositions containing alkenyl liquid crystals and having negative dielectric anisotropy, such as MLC-3022 and MLC-3023 (containing a photopolymerizable compound (RM)) manufactured by Merck & Co., Ltd., can be used.

[0196] Methods for sandwiching this liquid crystal layer between two substrates include known methods. For example, a method includes preparing a pair of substrates each having a liquid crystal alignment film, dispersing spacers such as beads on the liquid crystal alignment film of one substrate, applying an adhesive around the periphery of the substrate, and then bonding the other substrate to the substrate with the liquid crystal alignment film facing inward, and then injecting liquid crystal under reduced pressure to seal the resulting structure. Alternatively, a liquid crystal cell can also be produced by preparing a pair of substrates each having a liquid crystal alignment film, dispersing spacers such as beads on the liquid crystal alignment film of one substrate, dripping liquid crystal, and then bonding the other substrate to the substrate with the liquid crystal alignment film facing inward to seal the resulting structure. The thickness of the spacer in this case is preferably 1 to 30 μm, more preferably 2 to 10 μm.

[0197] The step of irradiating the liquid crystal alignment film and the liquid crystal layer with ultraviolet light to prepare a liquid crystal cell may be performed at any time after the liquid crystal is sealed in. The irradiation dose of ultraviolet light is, for example, 1 to 60 J / cm ２ , preferably 40 J / cm ２or less, and a lower dose of ultraviolet light can suppress a decrease in reliability caused by damage to components constituting the liquid crystal display element. The wavelength of the ultraviolet light used is preferably 300 to 500 nm, more preferably 300 to 400 nm. It is preferable that the wavelength of the ultraviolet light used in the process of preparing the liquid crystal cell is different from the wavelength of the ultraviolet light used in the light irradiation process. In particular, it is preferable that the wavelength of the ultraviolet light used in the process of preparing the liquid crystal cell is longer than the wavelength of the ultraviolet light used in the light irradiation process, from the viewpoint of preventing the reverse reaction of the light irradiation process from proceeding in the process of preparing the liquid crystal cell. For example, it is preferable that the wavelength of the ultraviolet light used in the light irradiation process is 300 to 350 nm, and the wavelength of the ultraviolet light used in the process of preparing the liquid crystal cell is 350 to 400 nm. This can avoid the problem of the reverse reaction of the photoalignable group proceeding and the loss of photoalignment during the PSA treatment after the photoalignment treatment.

[0198] The liquid crystal alignment film and the liquid crystal layer may be irradiated with ultraviolet light while applying a voltage and maintaining the electric field. The voltage applied between the electrodes is, for example, 5 to 30 Vpp, preferably 5 to 20 Vpp.

[0199] In the case of the PSA method, in which the liquid crystal contains a polymerizable compound, when ultraviolet light is irradiated onto the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and this polymer memorizes the direction in which the liquid crystal molecules tilt, thereby increasing the response speed of the resulting liquid crystal display element.

[0200] The liquid crystal aligning agent of the present invention is imparted with a tilt angle by the photo-alignment step, which is mediated by photoreaction of the photo-alignable groups of the polymer (component (A)). Subsequently, during PSA treatment, radicals are generated from the alkenyl liquid crystal in the liquid crystal composition, which then polymerizes, thereby fixing the imparted tilt angle. This improves the tilt angle durability of the resulting liquid crystal display element.

[0201] Furthermore, the liquid crystal aligning agent is not only useful as a liquid crystal aligning agent for producing vertical alignment type liquid crystal display elements such as PSA type liquid crystal displays and SC-PVA type liquid crystal displays, but can also be suitably used for producing liquid crystal alignment films formed by rubbing treatment or photo-alignment treatment.

[0202] The present invention will be described in more detail below with reference to examples, but the present invention should not be construed as being limited to these. The abbreviations of the compounds used and the methods for measuring each physical property are as follows. (Photoalignable Monomer) Of the photoalignable monomers listed below, HQ-1 to HQ-11 are included in the monomers represented by formula (1).

[0203]

[0204] (Thermal crosslinkable monomer)

[0205]

[0206] (Tetracarboxylic acid dianhydride)

[0207]

[0208] (diamine)

[0209]

[0210] (Crosslinking agent)

[0211]

[0212] (Monomer reaction reagent) Et ３ N: Triethylamine (polymerization initiator) V-601: 2,2'-azobis(isobutyrate) dimethyl (solvent) NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve THF: tetrahydrofuran DMF: N,N-dimethylformamide DMAc: N,N-dimethylacetamide

[0213] (Molecular Weight Measurement) The molecular weights of the polyamic acid and polyimide polymers in the synthesis examples were measured 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: Column temperature: 50°C, eluent: DMF (additive: lithium bromide monohydrate (LiBr.H ２ The following conditions were used: 0) 30 mmol / L, anhydrous crystalline phosphoric acid (o-phosphoric acid) 30 mmol / L, and THF 10 mL / L; flow rate: 1.0 mL / min. Standard samples for preparing a calibration curve: TSK standard polyethylene oxide (molecular weights: approximately 9,000,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation; and polyethylene glycol (molecular weights: approximately 12,000, 4,000, and 1,000) manufactured by Polymer Laboratory Co., Ltd. The molecular weight of the polymer obtained from the radical polymerizable monomer was measured using a room temperature gel permeation chromatography (GPC) apparatus (CBM-20A) manufactured by Shimadzu Corporation and a series of columns (Shodex (registered trademark) KF-804L and KF-803L) manufactured by Showa Denko K.K.) as follows. Column temperature: 40°C Eluent: tetrahydrofuran Flow rate: 1.0 mL / min Standard sample for preparing calibration curve: standard polystyrene (molecular weight: 197,000, 55,100, 12,800, 3,950, 1,260) (manufactured by Tosoh Corporation)

[0214] (Measurement of Imidization Ratio) The imidization ratio in the synthesis examples was measured as follows. 20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard, φ5, manufactured by Kusano Scientific Co., Ltd.), and deuterated dimethyl sulfoxide (DMSO-d ６1.0 mL of a mixture of 100% TMS and 0.05% TMS was added and sonicated to completely dissolve the solution. This solution was subjected to 500 MHz proton NMR measurement using a JEOL Datum NMR spectrometer (JNW-ECA500). A proton derived from a structure that remains unchanged before and after imidization was determined as the reference proton, and the imidization rate was calculated using the integrated peak value of this proton and the integrated peak value of a proton derived from the NH group of the amic acid that appears around 9.5 to 10.0 ppm, according to the following formula. In the formula, x is the integrated peak value of the proton derived from the NH group of the amic acid, y is the integrated peak value of the reference proton, and α is the ratio of the number of reference protons to one proton of the NH group of the amic acid in the case of polyamic acid (with an imidization rate of 0%). Imidization rate (%) = (1 - α x / y) x 100

[0215] [Synthesis of Photoreactive Monomers] HQ-1 to HQ-11 and AD-1 are novel compounds not disclosed in the literature, and the products in the following Synthesis Examples 1-1 to 1-12 are １ The product was identified by H-NMR analysis. The analysis conditions were as follows: Apparatus: BRUKER ADVANCE III-500 MHz Measurement solvent: deuterated chloroform (CDCl ３ ) Reference substance: tetramethylsilane (TMS) (δ 0.0 ppm for 1H)

[0216] <Synthesis Example 1-1: Synthesis of HQ-1>

[0217]

[0218] <<Synthesis of HQ-1-1>> THF (300 g) and DMF (0.05 g) were added to (2E)-3-[4-(trans-4-Pentylcyclohexyl)phenyl]-2-propenoic 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, and after completion of the dropwise addition, the mixture was stirred at room temperature of 25°C for 16 hours to allow the reaction to proceed. Stirring was stopped, and the reaction solution was concentrated to obtain HQ-1-1 (theoretical yield: 53.3 g).

[0219] <<Synthesis of HQ-1>> 4-Hydroxyphenyl methacrylate (32.8 g, 0.184 mol), THF (267 g) and Et ３ N (20.3 g, 0.201 mol) was added, and the mixture was stirred while cooling in an ice bath at 0°C. To this was added dropwise a solution of the above HQ-1-1 dissolved in THF (160 g), and after the completion of the dropwise addition, the mixture was stirred at room temperature (25°C) for 24 hours to cause a reaction. ２ The resulting crude product was added with 1275 g of HCl, and the mixture was stirred at room temperature (25°C) and washed with a slurry. The filtered crystals were then dried under reduced pressure to obtain HQ-1 (yield: 72.6 g, 0.158 mol, 94% yield over two steps). １ H-NMR (500MHz) in CDCl ３ : δ (ppm) = 7.85 (d, J = 16.0 Hz, 1H), 7.51 (d, J = 8.0 Hz, 2H), 7.27-7.2 3 (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).

[0220] <Synthesis Example 1-2: Synthesis of HQ-2>

[0221]

[0222] HQ-2 was obtained in the same manner as in Synthesis Example 1-1, except that (E)-3-(4-(((trans,trans)-4′-pentyl-[1,1′-bi(cyclohexane)]-4-carbonyl)oxy)phenyl)acrylic acid (HQ-2-0) was used instead of HQ-1-0. １ H-NMR (500MHz) in CDCl ３: δ (ppm) = 7.84 (d, J = 16.0 Hz, 1H), 7.60 (d, J = 8.5 Hz, 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).

[0223] <Synthesis Example 1-3: Synthesis of HQ-3>

[0224]

[0225] HQ-3 was obtained in the same manner as in Synthesis Example 1-1, except that (E)-3-(4-((trans,trans)-4′-pentyl-[1,1′-bi(cyclohexane)]-4-yl)phenyl)acrylic acid (HQ-3-0) was used instead of HQ-1-0. １ H-NMR (500MHz) in CDCl ３ : δ (ppm) = 7.85 (d, J = 15.0 Hz, 1H), 7.51 (d, J = 10.0 Hz, 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).

[0226] <Synthesis Example 1-4: Synthesis of HQ-4>

[0227]

[0228] HQ-4 was obtained in the same manner as in Synthesis Example 1-1, except that (E)-3-(4-(((trans,trans)-4'-(4,4,4-trifluorobutyl)-[1,1'-bi(cyclohexane)]-4-carbonyl)oxy)phenyl)acrylic acid (HQ-4-0) was used instead of HQ-1-0. １ H-NMR (500MHz) in CDCl ３ : δ (ppm) = 7.85 (d, J = 16.0 Hz, 1H), 7.60 (d, J = 8.5 Hz, 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), 2.1 8-2.15 (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).

[0229] <Synthesis Example 1-5: Synthesis of HQ-5>

[0230]

[0231] HQ-5 was obtained in the same manner as in Synthesis Example 1-1, except that (E)-3-(4-(trans-4-pentylcyclohexyl)phenyl)but-2-enoic acid (HQ-5-0) was used instead of HQ-1-0. １ H-NMR (500MHz) in CDCl ３ : δ (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 = 1.0Hz, 3 H), 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).

[0232] <Synthesis Example 1-6: Synthesis of HQ-6>

[0233]

[0234] HQ-6 was obtained in the same manner as in Synthesis Example 1-1, except that (E)-3-(4-(trans-4-propylcyclohexyl)phenyl)acrylic acid (HQ-6-0) was used instead of HQ-1-0. １ H-NMR (500MHz) in CDCl ３ : δ (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 = 16.0Hz, 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).

[0235] <Synthesis Example 1-7: Synthesis of HQ-7>

[0236]

[0237] <<Synthesis of HQ-7-0>> 1-Bromo-2-fluoro-4-(trans-4-pentylcyclohexyl)benzene (32.7 g, 100 mmol), acrylic acid (10.8 g, 150 mmol), tripropylamine (43.0 g, 300 mmol), and DMAc (100 g) were charged, and after nitrogen substitution, palladium acetate (0.45 g, 2.0 mmol) and tri(o-tolyl)phosphine (1.2 g, 4.0 mmol) were charged and stirred at 100°C. After completion of the reaction, the reaction solution was poured into a 1N aqueous hydrochloric acid solution (400 g), and the precipitate was filtered off and dried. THF (200 g) was added to the obtained crude product and dissolved at 45°C. After that, insoluble matter was filtered off, and the filtrate was concentrated. Ethyl acetate (250 g) was added to the obtained crude product and dissolved at 50°C, and then the product was cooled to 0°C, filtered, and dried to obtain HQ-7-0 (yield: 23.2 g, 0.073 mol, yield: 73%).

[0238] <<Synthesis of HQ-7>> HQ-7 was obtained in the same manner as in Synthesis Example 1-1, except that (E)-3-(2-fluoro-4-((1s,4r)-4-propylcyclohexyl)phenyl)acrylic acid (HQ-7-0) was used instead of HQ-1-0. １ H-NMR (500MHz) in CDCl ３ : δ (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).

[0239] <Synthesis Example 1-8: Synthesis of HQ-8>

[0240]

[0241] HQ-8 was obtained in the same manner as in Synthesis Example 1-1, except that (E)-2-methyl-3-(4-((1s,4r)-4-pentylcyclohexyl)phenyl)acrylic acid (HQ-8-0) was used instead of HQ-1-0. １ H-NMR (500MHz) in CDCl ３ : δ (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).

[0242] <Synthesis Example 1-9: Synthesis of HQ-9>

[0243]

[0244] <<Synthesis of HQ-9-0>> 1-Bromo-2-fluoro-4-(trans-4-pentylcyclohexyl)benzene (19.6 g, 60 mmol), methacrylic acid (20.7 g, 240 mmol), tripropylamine (51.6 g, 360 mmol), and DMAc (60 g) were charged, and after nitrogen substitution, palladium acetate (0.27 g, 1.2 mmol) and tri(o-tolyl)phosphine (0.73 g, 2.4 mmol) were charged and stirred at 130 ° C. After completion of the reaction, the reaction solution was poured into a 1N aqueous hydrochloric acid solution (240 g), and the precipitate was filtered off and dried. THF (160 g) was added to the obtained crude product and dissolved at 45 ° C., and then insoluble matter was filtered off, and the filtrate was concentrated. Ethyl acetate (120 g) was added to the obtained crude product and dissolved at 50°C, and then the product was cooled to 0°C, filtered, and dried to obtain HQ-9-0 (yield: 6.1 g, 0.018 mol, yield: 30%).

[0245] <<Synthesis of HQ-9>> HQ-9 was obtained in the same manner as in Synthesis Example 1-1, except that (E)-3-(2-fluoro-4-((1s,4r)-4-pentylcyclohexyl)phenyl)-2-methylacrylic acid (HQ-9-0) was used instead of HQ-1-0. １ H-NMR (500MHz) in CDCl ３ : δ (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).

[0246] <Synthesis Example 1-10: Synthesis of HQ-10>

[0247]

[0248] HQ-10 was obtained in the same manner as in Synthesis Example 1-1, except that 4-hydroxyphenyl acrylate was used instead of 4-hydroxyphenyl methacrylate. １ H-NMR (500MHz) in CDCl ３ : δ (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).

[0249] <Synthesis Example 1-11: Synthesis of HQ-11>

[0250]

[0251] <<Synthesis of HQ-11-1>> The steps up to HQ-1-1 were carried out in the same manner as in Synthesis Example 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 room temperature (25° C.). ３ N (11.5 g, 0.113 mol) was added dropwise, and after the completion of the dropwise addition, the mixture was stirred at room temperature of 25° C. for 21 hours. Ion-exchanged water (120 g) was added to the reaction mixture and stirred. ３ N HCl was dissolved. Ethyl acetate (120 g) was added, and the mixture was transferred to a separatory funnel and extracted with ethyl acetate, after which the aqueous phase was removed. The organic phase was concentrated to obtain a crude product. Methanol (90 g) was added to the obtained solid, and the mixture was stirred and slurry washed at room temperature (25°C), and the filtered solid was dried to obtain HQ-11-1. １ H-NMR (500MHz) in CDCl ３: δ (ppm) = 7.83 (d, J = 16.0 Hz, 1H), 7.50 (d, J = 8.2 Hz, 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).

[0252] HQ-11-1 (6.00 g, 0.0111 mol) was mixed with THF (30 g), Et ３ N (2.48 g, 0.0245 mol) was charged and stirred at room temperature of 25° C. Methacryloyl chloride (2.33 g, 0.0223 mol) was added dropwise, and after the completion of the dropwise addition, the mixture was stirred at 50° C. for 3 hours. ３ N (1.13 g, 0.0111 mol) and Methacryloyl chloride (1.17 g, 0.0111 mol) were further added, and the mixture was heated and stirred at 60°C for 17 hours, at which point the raw materials disappeared. Ion-exchanged water (90 g) was added to the reaction solution, and crystallization was carried out by water separation, and the crystallization was separated by filtration to obtain a crude product. Methanol (35 g) was added to the obtained crude product, and the mixture was stirred and slurry washed at room temperature of 25°C, and the solid was separated by filtration. THF (16 g) was added to the obtained solid to completely dissolve it, and after adding heptane (64 g), the THF was concentrated, and the precipitated white solid was separated by filtration and dried to obtain HQ-11. １ H-NMR (500MHz) in CDCl ３ : δ (ppm) = 7.84 (d, J = 16.0 Hz, 1H), 7.51 (d, J = 8.2 Hz, 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, 1H), 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).

[0253] <Synthesis Example 1-12: Synthesis of AD-1>

[0254]

[0255] AD-1 was obtained in the same manner as in Synthesis Example 1-1, except that 3-hydroxyadamantan-1-yl methacrylate was used instead of 4-hydroxyphenyl methacrylate. １ H-NMR (500MHz) in CDCl ３ : δ (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).

[0256] [Polymer Synthesis] <Synthesis Example 2-1> A 100 mL four-neck flask was charged with radically polymerizable monomers HQ-1 (2.30 g, 5.00 mmol), MA-1 (1.94 g, 22.5 mmol), and MA-2 (3.20 g, 22.5 mmol), and a radical polymerization initiator V-601 (0.576 g, 2.50 mmol) were dissolved in THF (30 g) to prepare a monomer mixture solution. The mixture solution was degassed using a diaphragm pump and then heated and stirred at 60°C for 18 hours to obtain polymer solution PM-1. The weight average molecular weight Mw measured in polystyrene equivalent terms by GPC was 43,000, and the molecular weight distribution Mw / Mn was 2.4.

[0257] Synthesis Examples 2-2 to 2-17 Polymer solutions PM-2 to 18 were obtained by carrying out the same operations as in Synthesis Example 2-1, except that the types and molar ratios of the monomers used were changed as shown in Table 1 below.

[0258]

[0259] <Synthesis Example 3-1> 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 to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature while feeding nitrogen to dissolve. Thereafter, CA-1 (18.8 g, 96.00 mmol) and NMP (75.3 g) were added under ice cooling, and the mixture was stirred at 40 ° C. for 12 hours to obtain a solution of polyamic acid (PAA-1) having a solids concentration of 20% by mass (viscosity: 833 mPa s).

[0260] Synthesis Examples 3-2 and 3-3 Polymer solutions PAA-2 and PAA-3 were obtained by carrying out the same operations as in Synthesis Example 3-1, except that the types and molar ratios of the monomers used were changed as shown in Table 2 below.

[0261] Synthesis Example 3-4 In a 300 mL four-neck 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 for 5 hours at 60 ° C. while feeding nitrogen. Thereafter, after cooling to 15 ° C., CA-1 (13.4 g, 68.5 mmol), CA-3 (5.22 g, 23.9 mmol) and NMP (43.8 g) were added, and the mixture was stirred for 10 hours at 40 ° C. to obtain a solution of polyamic acid having a solids concentration of 20% by mass (viscosity: 850 mPa s). The obtained polyamic acid solution (210 g) was weighed into a 300 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and NMP was added to a solids concentration of 6.5 mass %, followed by 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. This reaction solution was poured into methanol (2940 mL), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain a polyimide powder. The imidization rate of this polyimide powder was 75%. NMP was added to the obtained polyimide powder (2.00 g) to a solids concentration of 12 mass %, and the mixture was stirred and dissolved at 70°C for 2 hours to obtain a solution of polyimide (PI-1).

[0262] The specifications of the polyamic acids and polyimides obtained in Synthesis Examples 3-1 to 3-4 are shown in Table 2. In Table 2, the numerical values ​​for the tetracarboxylic acid components represent the amount (parts by mole) of each compound used relative to 100 parts by mole of the total amount of the tetracarboxylic acid components used in each polymerization step. The numerical values ​​for the diamine components represent the amount (parts by mole) of each compound used relative to 100 parts by mole of the total amount of the diamine components used in each polymerization step.

[0263]

[0264] Example 1 BCS was added to the polymer solution (PM-1) obtained in Synthesis Example 2-1, and THF was distilled off under reduced pressure to obtain a BCS solution of PM-1 with a solid content concentration of 20% by mass. Next, NMP and BCS were added as solvents to the BCS solution of PM-1 and stirred at room temperature to obtain a liquid crystal aligning agent AL-1 with a solvent composition of NMP:BCS=60:40 (mass ratio) and a polymer solid content concentration of 4% by mass.

[0265] Example 2 To 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, thereby obtaining a liquid crystal aligning agent AL-2 having a solvent composition of NMP:BCS=60:40 (mass ratio), a polymer solid content of 4 mass%, and CL-1 of 10 mass parts relative to 100 mass parts of polymer solid content.

[0266] Example 3 The solution of polyamic acid PAA-1 obtained in Synthesis Example 3-1 and NMP and BCS as solvents were added to the BCS solution of PM-1 obtained in Example 1, and the mixture was stirred at room temperature to obtain a liquid crystal aligning agent AL-3 having a solvent composition of NMP:BCS=60:40 (mass ratio), a polymer solid content concentration of 4 mass%, and a polymer solid content ratio of PM-1:PAA-1=15:85 (mass ratio).

[0267] (Examples 4 to 27 and Comparative Examples 1 to 5) As shown in Table 3, except for the point that the type of polymer solution and additives used were changed, the same procedures as in Examples 1 to 3 were carried out to obtain liquid crystal aligning agents (AL-4) to (AL-28), (AL-R1) to (AL-R6).

[0268]

[0269] <Preparation of Liquid Crystal Display Element> 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 each pressure-filtered through a membrane filter with a pore size of 1 μm. The resulting solution was spin-coated on the ITO surface of a glass substrate equipped with a transparent electrode made of an ITO film, dried on a hot plate at 70°C for 90 seconds, and then baked on a hot plate at 200°C for 30 minutes to form a liquid crystal alignment film with a film thickness of 100 nm. Next, the coated film surface was exposed to light via a polarizer at an irradiation intensity of 4.3 mW / cm.２ Linearly polarized ultraviolet light with a wavelength of 313 nm was applied at 50 mJ / cm from an angle inclined by 40° from the normal direction of the substrate. ２ The substrate was irradiated with light to obtain a substrate with a liquid crystal alignment film. Linearly polarized ultraviolet light was prepared by passing ultraviolet light from a high-pressure mercury lamp through a 313 nm bandpass filter and then through a 313 nm polarizing plate. Two of the above substrates were prepared. Bead spacers with a diameter of 4 μm were dispersed on the liquid crystal alignment film of one substrate, and then a sealant (Mitsui Chemicals, XN-1500T) was applied. The other substrate was then attached so that the liquid crystal alignment film faces faced each other and the alignment direction was 180°. The sealant was then thermally cured at 120°C for 90 minutes to produce an empty cell. Liquid crystal (Merck, MLC-3022) was injected into this empty cell using a reduced-pressure injection method to obtain a liquid crystal display device.

[0270] <Evaluation> (Liquid Crystal Alignment) The liquid crystal display element obtained above was subjected to isotropic phase treatment at 120°C for 1 hour, and then the cell was observed using a polarizing microscope. The evaluation criteria were "good" if there were no alignment defects such as light leakage or domain generation, and uniform liquid crystal driving was obtained when voltage was applied to the liquid crystal cell, and "poor" otherwise. The evaluation results are shown in Table 4.

[0271] (Pretilt Angle) The pretilt angle of the liquid crystal cell of the liquid crystal display element prepared above was measured by the Mueller matrix method using an AxoScan manufactured by Axometrics Inc. The evaluation results are shown in Table 4.

[0272] (Evaluation of Tilt Angle Change) After measuring the pretilt angle, a DC voltage of 15 V was applied to the liquid crystal cell, and the tilt angle was measured again after 24 hours to calculate the change in tilt angle. The evaluation results are shown in Table 4. The smaller the tilt angle change, the better the afterimage characteristics. Specifically, the tilt angle change is less than 0.05, preferably less than 0.04, and preferably 0.03 or less.

[0273] (Voltage Holding Ratio (VHR)) To evaluate VHR, a voltage of 4 V was applied to the liquid crystal cell prepared above for 60 μs at a temperature of 60° C., and the voltage after 16.67 ms was measured, and the extent to which the voltage was held was calculated as the voltage holding ratio. The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Corporation. The evaluation results are shown in Table 3.

[0274]

[0275] As shown in Table 4, comparing Examples 1, 11-19, 22-24, and 27-28 with Comparative Example 1, the liquid crystal alignment film obtained from the liquid crystal alignment agent using a photo-aligning monomer in which an aromatic group is directly bonded to the polymerizable functional group exhibited little tilt angle change, excellent image retention characteristics during AC drive, and excellent voltage holding ratio characteristics. On the other hand, the liquid crystal alignment film obtained from the liquid crystal alignment agent using a photo-aligning monomer in which an aromatic group is not directly bonded to the polymerizable functional group exhibited large tilt angle change and poor image retention characteristics during AC drive. Furthermore, comparing Example 1 with Comparative Example 5, the liquid crystal alignment film obtained from the liquid crystal alignment agent using a photo-aligning monomer in which the polymerizable functional group does not have a methacrylic group exhibited poor voltage holding ratio. Furthermore, comparing Example 2 with Comparative Example 2, even when a crosslinking agent was introduced, when a photo-aligning monomer in which an aromatic group is directly bonded to the polymerizable functional group was used, a liquid crystal alignment film was obtained with little tilt angle change, excellent image retention characteristics during AC drive, and excellent voltage holding ratio characteristics. In addition, a comparison with Examples 3 to 10, 20 to 21, 25 to 26, and Comparative Examples 3 and 4 revealed that this is also true when the present alignment agent is used in polymer blends with polyamic acid or polyimide that do not contain photoalignment groups, or when the type of crosslinker is changed, and that when a photoalignment monomer in which an aromatic group is directly bonded to a polymerizable functional group is used, a liquid crystal alignment film can be obtained that has little change in tilt angle, excellent afterimage characteristics when driven by AC, and excellent voltage holding ratio characteristics.

[0276] The liquid crystal aligning agent of the present invention and the liquid crystal display element using the liquid crystal alignment film obtained therefrom can be suitably used as a liquid crystal display element that requires durability, such as for use in a vehicle.

Claims

1. As the component (A), a compound represented by the following formula (1) (wherein R １１ represents a hydrogen atom or a methyl group; Ar represents an aromatic ring which may have a substituent; A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4-naphthylene, 2,6-naphthylene, or phenylene; A is optionally substituted with a fluorine atom, a chlorine atom, a cyano group, an alkoxy group having 1 to 5 carbon atoms, or a linear or branched alkyl residue, and the linear or branched alkyl residue is optionally substituted with one cyano group or one or more halogen atoms; R １ is a single bond, an oxygen atom, -COO- or -OCO-; R ２ is a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group, R ３ is a single bond, an oxygen atom, -COO- or -OCO-; R ４ is a monovalent organic group having 3 to 40 carbon atoms, including a linear or branched alkyl group having 1 to 40 carbon atoms or an alicyclic group, R ４ may be substituted with a fluorine atom, and D is an oxygen atom, a sulfur atom or -NR ｄ - (where R ｄ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a is an integer of 0 to 3, and when a is 2 or more, a plurality of R １ and R ２ are each independently defined as above. X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 3 carbon atoms, and some or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms. The "wavy lines" between "C" and "A", and between "C" and "X" mean that the polymer may be either an E-form or a Z-form. A liquid crystal aligning agent comprising a polymer obtained using a monomer represented by the formula (I) and a solvent.

2. The liquid crystal aligning agent according to claim 1, further satisfying at least one of the following requirements Z1 and Z2. Z1: The polymer (A) has a thermal crosslinkable group A and a thermal crosslinkable group B. Z2: The polymer (A) has a thermal crosslinkable group A, and further contains a compound having two or more thermal crosslinkable groups B in the molecule as a component (B). The thermal crosslinkable group A and the thermal crosslinkable group B are each independently an organic group selected from the group consisting of a carboxy group, a protected carboxy group, an amino group, a protected amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxy group, a protected hydroxy group, an epoxy group, an oxetanyl group, a thiiranyl group, an isocyanate group, and a blocked isocyanate group, and are selected so that the thermal crosslinkable group A and the thermal crosslinkable group B undergo a crosslinking reaction by heat. Here, when the thermal crosslinkable group A and the thermal crosslinkable group B are both self-crosslinkable groups, the thermal crosslinkable group A and the thermal crosslinkable group B may be the same as each other.

3. The monomer represented by formula (1) is represented by the following formula (1-1) (wherein Q １ is a hydrogen atom or a methyl group, and Q ２ is an alkyl group having 3 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms, X and Y are each independently a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group or a trifluoromethyl group, Z is a single bond, -O-, -COO- or -OCO-, Ar is an aromatic ring which may have a substituent, and n is 1 or 2. The liquid crystal aligning agent according to claim 1, which is a monomer represented by the following formula:

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

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

6. A liquid crystal display device comprising the liquid crystal alignment film according to claim 4.

7. A compound represented by the following formula (HQ): (In formula (HQ), Q １ is a hydrogen atom or a methyl group, and Q ２ is an alkyl group having 3 to 20 carbon atoms or a fluoroalkyl group having 1 to 20 carbon atoms, X and Y are each independently a hydrogen atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, or a trifluoromethyl group, Z is a single bond, -O-, -COO-, or -OCO-, A and B are each independently pyrimidine-2,5-diyl, pyridine-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4- or 2,6-naphthylene, or phenylene, which is optionally substituted with a fluorine atom, a chlorine atom, a cyano group, an alkoxy group having 1 to 5 carbon atoms, or a linear or branched alkyl residue (which is optionally substituted with one cyano group or one or more halogen atoms), and 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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