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

Abstract

Provided are a liquid crystal alignment film and a liquid crystal alignment agent which have good liquid crystal alignment properties, can impart a pretilt angle of 87-88 DEG, and can obtain high reliability. The present invention provides a liquid crystal aligning agent which contains (A) a polymer or a low-molecular-weight compound having a structure represented by formula (pa-1) (in the formula, A represents a pyrimidine-2, 5-diyl group or the like optionally substituted by a substituent group; r1 represents a single bond, an oxygen atom or the like; r2 represents a divalent aromatic group or the like; r3 represents a single bond, an oxygen atom or the like; r4 represents a monovalent organic group having 3-40 carbon atoms, including an alkyl group or the like; d represents an oxygen atom, a sulfur atom or the like; a represents an integer of 0-3; and * represents a bonding position. X and Y each independently represents a hydrogen atom, a fluorine atom or the like; (B) polymer (P) is at least one type selected from the group consisting of polyimide precursors and polyimides, the polyimide precursors being an imidized product of the polyimide precursors, and the polyimide precursors using a compound represented by formula (DA) (in the formula, X1 and X2 each independently represent a single bond, an ether bond or other bonding group; and n is an integer of 1-6. And Cy represents a non-aromatic cyclic group having a 7-20-membered ring. And R11 and R12 each independently represent a hydrogen atom or an alkyl group having 1-3 carbon atoms. ) and a diamine component of the diamine (0) represented by the formula (1). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film obtained therefrom, and a liquid crystal display element including 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 element having excellent display quality. Background Art

[0002] In a liquid crystal display element, a liquid crystal alignment film plays a role of aligning liquid crystals in a certain direction. Currently, the main liquid crystal alignment film used industrially is produced by coating a polyimide-based liquid crystal aligning agent formed from a solution of polyamic acid (also referred to as polyamic acid), polyamic acid ester, or polyimide, which is a polyimide precursor, on a substrate and forming a film. In addition, when making the liquid crystal align parallel or inclined with respect to the substrate surface, after film formation, a surface stretching treatment is further performed by rubbing.

[0003] On the other hand, when making the liquid crystal align perpendicular to the substrate (referred to as the vertical alignment (VA) method), a liquid crystal alignment film obtained by introducing a hydrophobic group such as a long-chain alkyl group, a cyclic group, or a combination of a cyclic group and an alkyl group (for example, refer to Patent Document 1), a steroid skeleton (for example, refer to Patent Document 2), etc. into the side chain of polyimide is used. At this time, when a voltage is applied between the substrates to make the liquid crystal molecules tilt in a direction parallel to the substrate surface, it is necessary to make the liquid crystal molecules tilt from the substrate normal direction to one direction in the substrate plane. As means for achieving this purpose, for example, the following methods have been proposed: a method of providing protrusions on the substrate; a method of providing slits on the display electrodes; a method of slightly pre-tilting (pretilting) the liquid crystal molecules from the substrate normal direction to one direction in the substrate plane by rubbing; and a method of adding a photopolymerizable compound to the liquid crystal composition in advance and using it together with a vertical alignment film such as polyimide, and irradiating ultraviolet rays while applying a voltage to the liquid crystal cell, thereby pretilting the liquid crystal (for example, refer to Patent Document 3), etc.

[0004] In recent years, as an alternative to the formation of protrusions or slits and the PSA technology method in liquid crystal alignment control, a method using an anisotropic photoreaction (photoalignment method) such as polarized ultraviolet irradiation has also been proposed. That is, it is known that by irradiating a polyimide film having photoreactive vertical alignment properties with polarized ultraviolet rays, alignment control ability and pretilt angle expressibility are imparted, and thus the tilt direction of liquid crystal molecules when a voltage is applied can be uniformly controlled (refer to Patent Document 4).

[0005] VA mode liquid crystal display elements are used in TVs and in-vehicle displays because of their high contrast ratio and large viewing angle. For liquid crystal display elements for TV use, backlights with high heat dissipation are used to obtain high brightness, or liquid crystal display elements used in in-vehicle applications, such as car navigation systems and instrument panels, are sometimes used or placed for a long time in high-temperature environments. Under such severe conditions, when the pretilt angle changes slowly, problems such as failure to obtain the initial display characteristics or uneven display may occur. In addition, the voltage holding characteristics and charge storage characteristics during liquid crystal driving are also affected by the liquid crystal alignment film, resulting in the following phenomena: when the voltage holding ratio is low, the contrast of the display screen decreases, and when the charge storage relative to the DC voltage is large, the display screen will burn in. In particular, in order to improve the transmittance, it is required to give a large pretilt angle of 2° or more from the vertical, and there has not been a material that can give such a large tilt angle by photoalignment treatment and can stably maintain the given tilt angle so far.

[0006] Prior art documents

[0007] Patent documents

[0008] Patent document 1: Japanese Patent Laid-Open No. 3-179323

[0009] Patent document 2: Japanese Patent Laid-Open No. 4-281427

[0010] Patent document 3: Japanese Patent No. 4504626

[0011] Patent document 4: Japanese Patent No. 4995267 Summary of the invention

[0012] Problems to be solved by the invention

[0013] As a result of research by the present inventors, when only the amount of the photoaligning group is adjusted, an inclination angle of 2° or more from the vertical cannot be stably generated. An object of the present invention is to provide a liquid crystal alignment film and a liquid crystal aligning agent that can stably generate an inclination angle of 2° or more from the vertical and can obtain high reliability.

[0014] Solutions for solving the problems

[0015] The present inventors have found the following <x>The technical solution as the main idea.

[0016] <x>A liquid crystal aligning agent containing a polymer or a low molecular compound as component (A), a polymer (P) as component (B), and a solvent, wherein the polymer or the low molecular compound has a photo-aligning group and a thermally crosslinkable group represented by the following formula (pa-1), the polymer (P) is at least one selected from the group consisting of a polyimide precursor and a polyimide, the polyimide is an imidized product of the polyimide precursor, and the polyimide precursor is obtained by using a diamine component containing a diamine (0) represented by the following formula (D A )).

[0017]

[0018] In formula (pa-1), A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4-naphthylene or phenylene, or 2,6-naphthylene or phenylene, which is optionally substituted by a group selected from a fluorine atom, a chlorine atom, a cyano group, or an alkoxy group having 1 to 5 carbon atoms, a linear alkyl residue or a branched alkyl residue (which is optionally substituted by 1 cyano group or 1 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, a divalent heterocyclic group or a divalent condensed ring group; R 3 is a single bond, an oxygen atom, -COO- or -OCO-; R 4 is a linear alkyl or branched alkyl having 1 to 40 carbon atoms, or a monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group; D represents an oxygen atom, a sulfur atom or -NR d - (wherein, R d represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms); a is an integer of 0 to 3; * represents a bonding position. When a is 2 or more, a plurality of R 1 and R 2 each independently have the above definitions. X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, and a part or all of the hydrogen atoms of the alkyl group are optionally substituted by fluorine atoms.

[0019] The "wavy line" between "C" and "A" and between "C" and "X" means that it can be the E isomer or the Z isomer. It should be noted that in this specification, the meaning of the "wavy line" is the same as above.

[0020]

[0021] In formula (D A ), X 1 and X 2 Each independently represents a single bond, an ether bond, -COO-, -OCO-, -NHCO-, -CONH-, a urethane bond, a urea bond, a thioether bond, -Si(R 1 )(R 2 )-(R 1 and R 2 each independently represent an alkyl group having 1 to 3 carbon atoms bonded to Si), -Si(R 3 )(R 4 )-O-(R 3 and R 4 each independently represent an alkyl group having 1 to 3 carbon atoms bonded to Si) and -N(R 5 )-(R 5 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms bonded to N); n is an integer of 1 to 6. Cy represents a non-aromatic cyclic group having 7 to 20 ring members (wherein when X 2 is a single bond, n is 0). R 11 and R 12 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0022] Effects of the Invention

[0023] By the present invention, a liquid crystal alignment film and a liquid crystal aligning agent capable of imparting a pretilt angle of 2° or more from vertical and capable of obtaining high reliability can be provided. In addition, a liquid crystal display element manufactured by the method of the present invention has excellent display characteristics. Detailed Embodiments

[0024] The liquid crystal aligning agent of the present invention contains a polymer or a low molecular compound as component (A), a polymer (P) as component (B), and a solvent. The polymer or the low molecular compound has a photo-aligning group and a thermally crosslinkable group represented by the following formula (pa-1). The polymer (P) is at least one selected from the group consisting of a polyimide precursor and a polyimide. The polyimide is an imidized product of the polyimide precursor, and the polyimide precursor is obtained by using a diamine component containing a diamine (0) represented by the formula (D A ).

[0025]

[0026] In formula (pa-1), A represents a pyrimidine-2,5-diyl, pyridine-2,5-diyl, thiophene-2,5-diyl, furan-2,5-diyl, 1,4-naphthylene or phenylene, or 2,6-naphthylene or phenylene which is optionally substituted by a group selected from a fluorine atom, a chlorine atom, a cyano group or is substituted by an alkoxy group having 1 to 5 carbon atoms, a linear alkyl residue or a branched alkyl residue (which is optionally substituted by 1 cyano group or 1 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, a divalent heterocyclic group or a divalent condensed ring group; R 3 is a single bond, an oxygen atom, -COO- or -OCO-; R 4 is a linear alkyl or branched alkyl having 1 to 40 carbon atoms, or a monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group; D represents an oxygen atom, a sulfur atom or -NR d -(wherein, R d represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms); a is an integer from 0 to 3; * represents a bonding position. When a is 2 or more, multiple R 1 and R 2 each independently have the above definitions. X and Y each independently are a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, and a part or all of the hydrogen atoms of the alkyl group are optionally substituted by fluorine atoms.

[0027] The "wavy line" between "C" and "A" and between "C" and "X" means that it can be the E isomer or the Z isomer.

[0028] When the component (A) is a polymer, the liquid crystal aligning agent can satisfy at least one of the following conditions Z1 and Z2.

[0029] Z1: The polymer as the component (A) has a thermally crosslinkable group A and a thermally crosslinkable group B.

[0030] Z2: The polymer as the component (A) has a thermally crosslinkable group A, and as the component (C), it further contains a compound having 2 or more thermally crosslinkable groups B in the molecule.

[0031] The thermally crosslinkable group A and the thermally crosslinkable group B are each independently an organic group selected from the group consisting of a carboxyl group, a protected carboxyl group, an amino group, a protected amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, a protected hydroxyl group, an epoxy group, an oxetanyl group, a thiiranyl group, an isocyanate group, and a blocked isocyanate group, and the thermally crosslinkable group A and the thermally crosslinkable group B are selected in such a way that a crosslinking reaction occurs by heat. Here, when both the thermally crosslinkable group A and the thermally crosslinkable group B are self-crosslinkable groups, the thermally crosslinkable group A and the thermally crosslinkable group B may be the same as each other optionally.

[0032] Here, "having two or more in the molecule" means the following: For example, in the case of containing two or more of the same groups such as two or more epoxy groups in the molecule, in addition, it also includes the case of containing two or more different groups in the molecule such as a combination of an epoxy group and a thiiranyl group. "Having two or more in the molecule" is preferably containing two or more of the same groups in the molecule.

[0033] The polymer as the component (A) contained in the liquid crystal aligning agent of the present invention has high sensitivity to light, and therefore, even in the case of irradiation with polarized ultraviolet rays of a low exposure amount, it can exhibit an alignment control ability.

[0034] In addition, by making the polymer as the component (A) contain the thermally crosslinkable group A and the component also contain the thermally crosslinkable group B, even when the firing time of the liquid crystal aligning agent is short, a crosslinking reaction of the polymer containing the component (A) can be achieved. Thus, when the photoalignment site exhibits anisotropy due to a photoreaction, anisotropy is likely to remain (be stored) in the liquid crystal alignment film, and therefore, the liquid crystal alignment property can be improved and a pretilt angle of the liquid crystal can be exhibited.

[0035] In addition, the liquid crystal aligning agent of the present invention can achieve the impartation of a pretilt angle of 2° or more from self-vertical by containing the polymer (P) as the component (B). The diamine (0) can improve the compatibility of the polymer (P) with the polymer or the low molecular compound as the component (A) due to its highly lipophilic structure. Since the diamine (0) itself does not exhibit vertical alignment property, a larger pretilt angle can be exhibited by using the diamine (0) exposed to the surface layer of the alignment film.

[0036] It should be noted that when the component (A) is a polymer, the photoalignment group, the thermally crosslinkable group A, and the thermally crosslinkable group B represented by the above formula (pa-1) can all be side chains in the polymer, and therefore, they can also be referred to as "side chains" as needed.

[0037] Hereinafter, each constitutional condition of the present invention will be described in detail.

[0038] <(Component (A): Specific polymer or low molecular compound)>

[0039] [Photo-orienting group represented by formula (pa-1)]

[0040] In the present invention, the part having the photo-orienting group represented by the above formula (pa-1) in the molecule can be represented by, for example, the following formula (a-1). In addition, the structure derived from the monomer represented by the following formula (a-1-m) can be cited, but it is not limited thereto.

[0041] In the following formula (a-1) or (a-1-m), I a is a monovalent organic group represented by the above formula (pa-1); S a represents a spacer unit, and it means that S a the bonding group on the left is optionally bonded to the main chain of a specific polymer via a spacer.

[0042] --S a --I a (a-1)

[0043]

[0044] S a can be represented by a structure such as the following formula (Sp).

[0045]

[0046] In formula (Sp),

[0047] W 1 the left bond represents the bond bonded to M b the bond,

[0048] W 3 the right bond represents the bond bonded to I a the bond,

[0049] W 1 、W 2 and W 3 each independently represents a single bond, a divalent heterocycle, -(CH 2 ) n -(wherein n represents 1 to 20), -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF 2 O-, -OCF 2 -, -CF 2 CF 2 -, or -C≡C-, and one or more non-adjacent CH 2 groups in these substituents can be independently replaced by -O-, -CO-, -CO-O-, -O-CO-, -Si(CH 3 ) 2 -O-Si(CH 3 ) 2 -, -NR-, -NR-CO-, -CO-NR-, -NR-CO-O-, -OCO-NR-, -NR-CO-NR-, -CH=CH-, -C≡C- or -O-CO-O- (wherein, R independently represents hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms), and is substituted,

[0050] A 1 and A 2 are each independently a single bond or a group selected from an alkylene group, a divalent aromatic group, a divalent alicyclic group or a divalent heterocyclic group, and each group may be unsubstituted or one or more hydrogen atoms may be optionally substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group.

[0051] In the formula (a-1-m), M a represents a polymerizable group. Examples of such polymerizable groups include (meth)acrylate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, free-radical polymerizable groups of (meth)acrylamide and its derivatives, and siloxane. Preferred examples include (meth)acrylate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, acrylamide.

[0052] r is an integer satisfying 1 ≤ r ≤ 3.

[0053] M b is a group selected from a single bond, an (r + 1)-valent heterocycle, an (r + 1)-valent linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms, an (r + 1)-valent aromatic group, and an (r + 1)-valent alicyclic group, and each group may be unsubstituted or one or more hydrogen atoms may be optionally substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group. Among them, when r is 2 or more, M b is a group other than the above single bond.

[0054] As the aromatic group in A 1 , A 2 and M b , examples include aromatic hydrocarbon groups having 6 to 18 carbon atoms such as a benzene ring, a biphenyl structure, and a naphthalene ring. As the alicyclic group in A 1 , A 2 and M b , examples include alicyclic hydrocarbon groups having 6 to 12 carbon atoms such as a cyclohexane ring and a dicyclohexane structure. As the alicyclic group in A 1 , A 2 and M b Among the heterocyclic groups, nitrogen-containing heterocyclic groups such as a pyridine ring, a piperidine ring, and a piperazine ring can be mentioned. As A 1 and A 2 Among the alkylene groups, linear alkylene groups or branched alkylene groups having 1 to 10 carbon atoms can be mentioned, etc.

[0055] From the viewpoint of being able to exhibit good vertical alignment control ability and stable pretilt angle, the group represented by the above (pa-1) is preferably the group represented by the following (pa-1-a). In addition, in the case where the component (A) is a polymer, the structure derived from the monomer represented by the following formula (pa-1-ma) can be mentioned, but it is not limited thereto.

[0056]

[0057] In formula (pa-1-a) or (pa-1-ma), M a and M b and S a Have the same definitions as above.

[0058] In addition, Z is an oxygen atom or a sulfur atom.

[0059] X a and X b 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.

[0060] R 1 Is a single bond, an oxygen atom, -COO-, or -OCO-.

[0061] R 2 Is a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group.

[0062] R 3 Is a single bond, an oxygen atom, -COO-, or -OCO-.

[0063] R 4 Is a linear alkyl group or a branched alkyl group having 1 to 40 carbon atoms, or a monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group.

[0064] R 5 Is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom, or a cyano group, preferably a methyl group, a methoxy group, or a fluorine atom.

[0065] a is an integer of 0 to 3, and b is an integer of 0 to 4.

[0066] In formula (pa-1-a) or (pa-1-ma), as S a The alkylene group is preferably a straight-chain or branched alkylene group having 1 to 8 carbon atoms, and is preferably, for example, methylene, ethylene, n-propylene, n-butylene, tert-butylene, n-pentylene, n-hexylene, n-heptylene, or n-octylene.

[0067] As S a Examples of the divalent aromatic group include 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, and the like.

[0068] In formula (pa-1-a) or (pa-1-ma), as S a Examples of the divalent alicyclic group include trans-1,4-cyclohexylene, trans-trans-1,4-bicyclohexylene, and the like.

[0069] As S a Examples of the divalent heterocyclic group include pyridine-2,6-diyl, pyridine-3,5-diyl, furan-2,5-diyl, piperazine-1,4-diyl, piperidine-1,4-diyl, and the like.

[0070] S a S is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and further preferably an alkylene group having 1 to 4 carbon atoms.

[0071] As R 2 Examples of the divalent aromatic group include 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, naphthylene, and the like.

[0072] As R 2 Examples of the divalent alicyclic group include trans-1,4-cyclohexylene, trans-trans-1,4-bicyclohexylene, and the like.

[0073] As R 2 Examples of the divalent heterocyclic group include pyridine-2,6-diyl, pyridine-3,5-diyl, furan-2,5-diyl, piperazine-1,4-diyl, piperidine-1,4-diyl, and the like.

[0074] R 2 R is preferably 1,4-phenylene, trans-1,4-cyclohexylene, or trans-trans-1,4-bicyclohexylene.

[0075] As R 4 A linear or branched alkyl group having 1 to 40 carbon atoms, examples thereof include a linear or branched alkyl group having 1 to 20 carbon atoms, and part or all of the hydrogen atoms of the alkyl group may be optionally substituted with fluorine atoms. Examples of the alkyl group include, for example, methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, 4,4,4-trifluorobutyl, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl, 3,3,4,4,5,5,5-heptafluoropentyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluorooctyl)ethyl, 2-(perfluorodecyl)ethyl and the like.

[0076] As R 4 A monovalent organic group having 3 to 40 carbon atoms containing an alicyclic group, examples thereof include cholestenyl group, cholestanyl group, adamantyl group, a group 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, the alkyl group having 1 to 20 carbon atoms may be optionally substituted with fluorine atoms, and * represents a bonding position) and the like.

[0077]

[0078] As the monomer represented by the above formula (pa-1-ma), structures represented by the formulas (paa-1-ma1) to (paa-1-ma18) can be cited, but are not limited thereto. It should be noted that in the formula, "E" represents the E isomer, and "t" represents that the cyclohexyl group is in the trans form.

[0079]

[0080]

[0081] [Thermal crosslinkable group A and thermal crosslinkable group B]

[0082] The thermal crosslinkable group A and the thermal crosslinkable group B are each independently an organic group selected from the group consisting of a carboxyl group, a protected carboxyl group, an amino group, a protected amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, a protected hydroxyl group, an epoxy group, an oxetanyl group, a thiiranyl group, an isocyanate group and a blocked isocyanate group, and the thermal crosslinkable group A and the thermal crosslinkable group B are selected in such a way that a crosslinking reaction occurs by heat, wherein the thermal crosslinkable group A and the thermal crosslinkable group B may be optionally the same as each other.

[0083] The protecting groups of the protected carboxyl group, protected amino group, and protected hydroxyl group in the thermally crosslinkable group A and the thermally crosslinkable group B are preferably protecting groups that are detached by heat.

[0084] Examples of the protecting group for the carboxyl group include acetal-based protecting groups such as methoxymethyl, ethoxyethyl, and 2-tetrahydropyranyl; cyclic alcohol-based protecting groups, etc.

[0085] Examples of the protecting group for the hydroxyl group include ether-based protecting groups such as methyl, ethyl, tert-butyl, benzyl, p-methoxybenzyl, and trityl; acetal-based protecting groups such as methoxymethyl, ethoxyethyl, and 2-tetrahydropyranyl; acyl-based protecting groups such as acetyl, pivaloyl, benzoyl, and trichloroacetyl; allyl-based protecting groups such as allyl and methallyl; carbamate-based protecting groups such as tert-butoxycarbonyl; and silyl ether-based protecting groups such as trimethylsilyl, triethylsilyl, and tert-butyldimethylsilyl.

[0086] Examples of the protecting group for the amino group include carbamate-based protecting groups such as tert-butoxycarbonyl, benzyloxycarbonyl, 1,1-dimethyl-2-haloethoxycarbonyl, 1,1-dimethyl-2-cyanoethoxycarbonyl, 9-fluorenylmethoxycarbonyl, allyloxycarbonyl, and 2-(trimethylsilyl)ethoxycarbonyl; amide-based protecting groups, imide-based protecting groups, sulfonamide-based protecting groups, etc.

[0087] Examples of the combination of such a thermally crosslinkable group A and a thermally crosslinkable group B are: a combination in which one is a carboxyl group or a protected carboxyl group and the other is an epoxy group, oxetanyl group, thiiranyl group, or blocked isocyanate group; a combination in which one is a hydroxyl group or a protected hydroxyl group and the other is a blocked isocyanate group; a combination in which one is a phenolic hydroxyl group or a phenolic protected hydroxyl group and the other is an epoxy group, oxetanyl group, or 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 are a carboxyl group and an epoxy group, a hydroxyl group and a blocked isocyanate group, etc.

[0088] In order to introduce the thermally crosslinkable group A into the polymer as the component (A), it is sufficient to copolymerize a monomer having the thermally crosslinkable group A.

[0089] In addition, when the liquid crystal aligning agent of the present invention satisfies the condition Z1, when producing the polymer as the component (A), it is sufficient to copolymerize both a monomer having the thermally crosslinkable group A and a monomer having the thermally crosslinkable group B.

[0090] Examples of the monomer having a thermally crosslinkable group include monomers having a carboxyl 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;

[0091] monomers having a hydroxyl 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, ε-caprolactone 2-(acryloyloxy)ethyl ester, ε-caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxy-norbornene-2-carboxylic acid 6-lactone, and 5-methacryloyloxy-6-hydroxy-norbornene-2-carboxylic acid 6-lactone;

[0092] monomers having a phenolic hydroxyl group such as hydroxystyrene, N-(hydroxyphenyl) methacrylamide, N-(hydroxyphenyl) acrylamide, N-(hydroxyphenyl) maleimide, and N-(hydroxyphenyl) maleimide;

[0093] monomers having an amino group such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate;

[0094] (meth)acrylamide compounds substituted with a hydroxymethyl or an alkoxymethyl group such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide;

[0095] monomers having an epoxy group such as allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl 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-vinyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide;

[0096] 3-(acryloxymethyl)oxetane, 3-(acryloxymethyl)-2-methyloxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(acryloxymethyl)-2-trifluoromethyloxetane, 3-(acryloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloxymethyl)-2-phenyloxetane, 3-(acryloxymethyl)-2,2-difluoroxetane, 3-(acryloxymethyl)-2,2,4-trifluoroxetane, 3-(acryloxymethyl)-2,2,4,4-tetrafluoroxetane, 3-(2-acryloxyethyl)oxetane, 3-(2-acryloxyethyl)-2-ethyloxetane, 3-(2-acryloxyethyl)-3-ethyloxetane, 3-(2-acryloxyethyl)-2-trifluoromethyloxetane, 3-(2-acryloxyethyl)-2-pentafluoroethyloxetane, 3-(2-acryloxyethyl)-2-phenyloxetane, 3-(2-acryloxyethyl)-2,2-difluoroxetane, 3-(2-acryloxyethyl)-2,2,4-trifluoroxetane, 3-(2-acryloxyethyl)-2,2,4,4-tetrafluoroxetane, 3-(methacryloxymethyl)oxetane, 3-(methacryloxymethyl)-2-methyloxetane, 3-(methacryloxymethyl)-3-ethyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloxymethyl)-2-phenyloxetane, 3-(methacryloxymethyl)-2,2-difluoroxetane, 3-(methacryloxymethyl)-2,2,4-trifluoroxetane, 3-(methacryloxymethyl)-2,2,4,4-tetrafluoroxetane, 3-(2-methacryloxyethyl)oxetane, 3-(2-methacryloxyethyl)-2-ethyloxetane, 3-(2-methacryloxyethyl)-3-ethyloxetane, 3-(2-methacryloxyethyl)-2-trifluoromethyloxetane, 3-(2-methacryloxyethyl)-2-pentafluoroethyloxetane, 3-(2-methacryloxyethyl)-2-phenyloxetane, 3-(2-methacryloxyethyl)-2,2-difluoroxetane, 3-(2-methacryloxyethyl)-2,2,4-trifluoroxetane, 3-(2-methacryloxyethyl)-2,2,4,4-tetrafluoroxetane and other monomers with an oxetanyl group;

[0097] Monomers having an episulfide group such as 2,3-epithiopropyl acrylate or 2,3-epithiopropyl methacrylate, and 2- or 3- or 4-(β-epithiopropylthiomethyl)styrene, 2- or 3- or 4-(β-epithiopropyl oxymethyl)styrene, 2- or 3- or 4-(β-epithiopropylthio)styrene, 2- or 3- or 4-(β-epithiopropyl oxy)styrene, etc.;

[0098] Monomers having a blocked isocyanate group such as 2-(0-(1'-methylpropylideneamino)carboxylamino)ethyl acrylate, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl acrylate, 2-(0-(1'-methylpropylideneamino)carboxylamino)ethyl methacrylate, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate, etc. It should be noted that (meth)acrylamide refers to both acrylamide and methacrylamide.

[0099] In addition, when obtaining a specific copolymer in the present invention, in addition to the monomer having a photo-orienting group represented by the above formula (a-1-m) and the monomer having a thermally crosslinkable group A and, if necessary, a thermally crosslinkable group B, other monomers copolymerizable with these monomers can also be used in combination.

[0100] Specific examples of such other monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, acrylamide compounds such as acrylamide, and monomers having a nitrogen-containing aromatic heterocyclic group and a polymerizable group.

[0101] Examples of acrylate compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracenylmethyl 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, etc.

[0102] Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, cetyl methacrylate, stearyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracenylmethyl 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, 8-ethyl-8-tricyclodecyl methacrylate, and the like.

[0103] Examples of the aforementioned (meth)acrylamide compound include acrylamide, methacrylamide, N-methylmethacrylamide, N,N-dimethylmethacrylamide, N,N-diethylmethacrylamide, and the like.

[0104] Examples of the aforementioned vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-vinyl-7-oxabicyclo[4.1.0]heptane, and the like.

[0105] Examples of the aforementioned styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

[0106] Examples of the aforementioned maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

[0107] The nitrogen-containing aromatic heterocycle may be an aromatic cyclic hydrocarbon containing at least 1, preferably 1 to 4, structures selected from the group consisting of the following formulas [N-a] to [N-b] (wherein Z 2 is a linear or branched alkyl group having 1 to 5 carbon atoms).

[0108]

[0109] Specifically, 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, an acridine ring, and the like. Further, the carbon atoms of these nitrogen-containing aromatic heterocycles may optionally have a substituent containing a heteroatom. Examples of the substituent containing a heteroatom include a pyridine ring.

[0110] 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, 2-(4-pyridylcarbonyloxy)ethyl (meth)acrylate, and the like.

[0111] As for the other monomers used in the present invention, one kind can be used alone, or two or more kinds of monomers can be used in combination.

[0112] The photoreactive moieties represented by the above formula (pa-1) contained in the polymer as the component (A) of the liquid crystal aligning agent of the present invention can be used alone, or two or more moieties can be used in combination.

[0113] The photoreactive moieties represented by the above formula (pa-1) are preferably contained in a proportion of 5 to 95 mol%, 10 to 60 mol%, or 15 to 50 mol% of all the repeating units of the polymer as the component (A).

[0114] The moieties having a thermally crosslinkable group contained in the polymer of the present invention can use the thermally crosslinkable group A alone, or two or more moieties including the thermally crosslinkable group A and the thermally crosslinkable group B can be used in combination.

[0115] The introduction amount of the moieties having a thermally crosslinkable group is preferably 5 to 95 mol%, 40 to 90 mol%, or 50 to 85 mol% of all the repeating units of the polymer as the component (A).

[0116] The content of the structure derived from the above other monomers is preferably 0 to 40 mol%, 0 to 30 mol%, or 0 to 20 mol% of all the repeating units of the polymer as the component (A).

[0117] <Manufacturing method of a specific polymer>

[0118] The specific polymer of the component (A) contained in the liquid crystal aligning agent of the present invention can be obtained by copolymerizing the monomer having a photo-orienting group represented by the above formula (pa-1), the monomer having a thermally crosslinkable group A, and, if desired, the monomer having a thermally crosslinkable group B. In addition, it can be copolymerized with the above other monomers.

[0119] Regarding the manufacturing method of the specific polymer of the component (A) in the present invention, there is no particular limitation, and a general method used industrially can be utilized. Specifically, it can be manufactured by cationic polymerization, radical polymerization, or anionic polymerization using the vinyl group of the monomer. Among these, from the viewpoint of ease of reaction control and the like, radical polymerization is particularly preferred.

[0120] As a polymerization initiator for radical polymerization, known compounds such as radical polymerization initiators and reversible addition-fragmentation chain transfer (RAFT) polymerization reagents can be used.

[0121] A radical thermal polymerization initiator is a compound that generates radicals by heating to a temperature above the decomposition temperature. Examples of such radical thermal polymerization initiators include, for example, peroxydiketones (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.), peroxoketals (dibutyl peroxycyclohexane, etc.), alkyl peresters (tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile and 2,2'-bis(2-hydroxyethyl)azobisisobutyronitrile, etc.).

[0122] Such a radical thermal polymerization initiator can be used alone as one kind, or two or more kinds can be used in combination.

[0123] The radical photoinitiator is not particularly limited as long as it is a compound that initiates radical polymerization upon light irradiation. Examples of such radical photoinitiators include known compounds such as benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, and isopropylxanthone. These compounds can be used alone or two or more kinds can be mixed and used.

[0124] The radical polymerization method is not particularly limited, and emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, etc. can be used.

[0125] The solvent used in the polymerization reaction of the specific polymer as the component (A) is not particularly limited as long as it is a solvent in which the generated polymer dissolves. As specific examples, solvents described in the later <Solvent> section can be cited, such as N-alkyl-2-pyrrolidones, dialkylimidazolidinones, lactones, carbonates, ketones, the compound represented by the formula (Sv-1) and the compound represented by the formula (Sv-2), tetrahydrofuran, 1,4-dioxane, dimethyl sulfone, dimethyl sulfoxide, etc.

[0126] These solvents can be used alone or mixed and used. Furthermore, even a solvent that does not dissolve the generated polymer can be mixed with the above solvents within the range where the generated polymer does not precipitate and used.

[0127] In addition, in radical polymerization, oxygen in the solvent can cause hindrance to the polymerization reaction. Therefore, the organic solvent is preferably a solvent degassed to the extent possible.

[0128] The polymerization temperature during radical polymerization can be selected from any temperature in the range of 30 to 150 °C, preferably in the range of 50 to 100 °C. In addition, the reaction can be carried out at any concentration. 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 in the initial stage of the reaction, and then an organic solvent can be added additionally.

[0129] In the above radical polymerization reaction, if the ratio of the radical polymerization initiator is relatively large with respect to the monomer, the molecular weight of the resulting polymer becomes small, and if it is small, the molecular weight of the resulting polymer becomes large. Therefore, the ratio of the radical initiator with respect to the polymerizable monomer is preferably 0.1 to 10 mol%. In addition, various monomer components, solvents, initiators, etc. can be added during the polymerization.

[0130] [Recovery of Polymer]

[0131] When recovering the polymer formed from the reaction solution obtained through the above reaction, it is only necessary to pour the reaction solution into a poor solvent to precipitate these polymers. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water, etc. The polymer precipitated by being poured into the poor solvent can be dried at normal temperature or by heating under normal pressure or reduced pressure after being recovered by filtration. In addition, if the operation of dissolving the precipitated and recovered polymer in an organic solvent again and then precipitating and recovering it is repeated 2 to 10 times, the impurities in the polymer can be reduced. Examples of the poor solvent at this time include, for example, alcohols, ketones, hydrocarbons, etc. If three or more poor solvents selected from them are used, the purification efficiency is further improved, so it is preferred.

[0132] Regarding the molecular weight of the specific polymer of component (A), considering the strength of the resulting coating film, the workability during film formation, and the uniformity of the coating film, the weight-average molecular weight measured by gel permeation chromatography (GPC) is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.

[0133] <Low-Molecular Compound as Component (A)>

[0134] When the component (A) is a low-molecular compound having a photo-orienting group and a thermo-crosslinking group represented by the formula (pa-1), as such a low-molecular compound, preferably, it is a compound having a molecular weight of 2000 or less, and while the compound has a photo-orienting group represented by the formula (pa-1), as a thermo-crosslinking group, it has a group capable of reacting with a carboxyl group to form a covalent bond.

[0135] The photo-orienting groups when the component (A) is a low-molecular compound having a photo-orienting group and a thermo-crosslinking group represented by the formula (pa-1) are as described above including preferred examples.

[0136] As the thermo-crosslinking group when the component (A) is a low-molecular compound having a photo-orienting group and a thermo-crosslinking group represented by the formula (pa-1), organic groups selected from the group consisting of an epoxy group, an oxetanyl group, a thiiranyl group, and a cyclic carbonate group can be cited.

[0137] Regarding the low-molecular compound as the component (A), compounds represented by the formulas (paa-1-mb1) to (paa-1-mb22) can be cited, but are not limited to them. It should be noted that in the formulas, "(E)" represents the E isomer, "(E,Z)" represents the E isomer or the Z isomer, and "t" represents that the cyclohexyl group is in the trans form.

[0138]

[0139]

[0140] The low-molecular compound as the component (A) can be produced by combining known reactions.

[0141] <Component (B)>

[0142] The component (B) contained in the liquid crystal aligning agent of the present invention is at least one polymer (P) selected from the group consisting of a polyimide precursor and a polyimide, and the polyimide precursor is obtained by using a diamine component containing a diamine (0) represented by the formula (D A ), and the polyimide is an imidized product of the polyimide precursor.

[0143] <Specific diamine>

[0144] As described above, the liquid crystal aligning agent of the present invention is characterized in that it contains a polymer (P) which is at least one selected from the group consisting of a polyimide precursor and a polyimide, the polyimide precursor is obtained by using a diamine component containing a diamine (0) (also referred to as a specific diamine in the present invention) represented by the following formula (D A ), and the polyimide is an imidized product of the polyimide precursor.

[0145]

[0146] In the above formula (D A ), X 1 , X 2 , n, Cy, R 11 and R 12 are as defined above, respectively.

[0147] In the above formula (D A ), from the viewpoints of ease of synthesis and the like, X 1 is preferably an ether bond, -COO-, -OCO-.

[0148] In the above formula (D A ), from the viewpoints of ease of synthesis and the like, X 2 is preferably an ether bond, -COO-, -OCO-.

[0149] In the above formula (D A ), when X 2 is a single bond, n is 0, and when X 2 is a bonding group, from the viewpoint of liquid crystal alignment, n is preferably 2 to 4.

[0150] In the above formula (D A ), R 11 and R 12 are preferably a hydrogen atom or a methyl group.

[0151] When the portion bonded with X 1 is defined as the 1-position, the substitution positions of the amino group on the benzene ring in the above formula (D A ) are preferably the 2,4-positions or the 3,5-positions.

[0152] As a preferred example of the above formula (D A ), the following formulas (d A -1) to (d A -3) can be cited.

[0153]

[0154] The diamine (0) represented by the formula (D A ) can be produced by using commercially available materials or publicly known materials and combining publicly known reactions.

[0155] <Polymer (P)>

[0156] The polymer (P) contained in the liquid crystal aligning agent of the present invention is a polyimide precursor or a polyimide which is an imidized product of the polyimide precursor, and the polyimide precursor is obtained by using a diamine component containing the above diamine (0). Here, the polyimide precursor is a polymer that can be imidized by polyamic acid, polyamic acid ester, etc. to obtain polyimide.

[0157] The polyamic acid (P') which is the polyimide precursor of the above polymer (P) can be obtained by the polymerization reaction of a diamine component containing the above diamine (0) and a tetracarboxylic acid component. The above diamine (0) can be used alone or in combination of two or more.

[0158] The amount of the diamine (0) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more based on all the diamine components.

[0159] The diamine component for producing the above polyamic acid (P') may contain a diamine other than the diamine (0) (hereinafter also referred to as other diamine). When other diamine is used in combination with the above diamine (0), the amount of the diamine (0) based on the diamine component is preferably 95 mol% or less, preferably 90 mol% or less, and more preferably 80 mol% or less.

[0160] Examples of the other diamine are listed below, but are not limited thereto. The above other diamine can be used alone or in combination of two or more. p-Phenylenediamine, 2,3,5,6-Tetramethyl-p-phenylenediamine, 2,5-Dimethyl-p-phenylenediamine, m-Phenylenediamine, 2,4-Dimethyl-m-phenylenediamine, 2,5-Diaminotoluene, 2,6-Diaminotoluene, 2,2'-Dimethyl-4,4'-diaminobiphenyl, 3,3'-Dimethyl-4,4'-diaminobiphenyl, 3,3'-Dimethoxy-4,4'-diaminobiphenyl, 3,3'-Dihydroxy-4,4'-diaminobiphenyl, 2,2'-Difluoro-4,4'-diaminobiphenyl, 3,3'-Difluoro-4,4'-diaminobiphenyl, 2,2'-Bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-Bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-Diaminobiphenyl, 4,4'-Diaminobiphenyl, 3,3'-Diaminobiphenyl, 2,2'-Diaminobiphenyl, 2,3'-Diaminobiphenyl, the following formula (d AL -1) to (d AL The diamines shown in (-10), 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, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)diphenyl ether, 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, 1,2-bis(6-amino-2-naphthyloxy)ethane, 1,2-bis(6-amino-2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 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; diamines having a photo-orienting group such as 4,4'-diaminoazobenzene or diaminotolanes; diamines having a photopolymerizable group at the terminal such as 2-(2,4-diaminophenoxy)ethyl methacrylate or 2,4-diamino-N,N-diallylaniline; diamines having a function of a radical polymerization initiator such as 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone or 2-(4-(2-hydroxy-2-methylpropanoyl)phenoxy)ethyl 3,5-diaminobenzoate; diamines having an amide bond such as 4,4'-diaminobenzanilide, diamines having a urea bond such as 1,3-bis(4-aminophenyl)urea, 1,3-bis(4-aminobenzyl)urea, 1,3-bis(4-aminophenethyl)urea;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, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene; 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N-[3-(1H-imidazol-1-yl)propyl]-3,5-diaminobenzamide, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl]-aniline or a heterocyclic-containing diamine such as a diamine represented by the following formula (z-1) to formula (z-13); or a diamine having a diphenylamine structure represented by 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine or N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-benzenediamine, etc., which has at least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary amino group and a tertiary amino group (hereinafter also referred to as a specific nitrogen atom-containing structure) (the amino group in the molecule does not have a protecting group bonded thereto that is removed by heating and replaced with a hydrogen atom); 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diamino-3,3'-dihydroxybiphenyl;Diamines having a carboxyl group such as 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 1,2-bis(4-aminophenyl)ethane-3-carboxylic acid, 4,4'-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, 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid; 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine; diamines having a group "-N(D)-" (where D represents a protecting group that is cleaved upon heating and replaced with a hydrogen atom, preferably a carbamate-based protecting group, more preferably tert-butoxycarbonyl) such as those represented by the following formulas (5-1) to (5-6); diamines having a steroid skeleton such as cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanosteryl 3,5-diaminobenzoate, and 3,6-bis(4-aminobenzoyloxy)cholestane, and diamines represented by the following formulas (V-1) to (V-2); diamines having a siloxane bond such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane; m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and diamines having two amino groups bonded to a group represented by any one of the formulas (Y-1) to (Y-167) described in International Publication No. 2018 / 117239;

[0161]

[0162]

[0163] In the above formula (V-1), m and n are each independently an integer from 0 to 3, satisfying 1 ≤ m + n ≤ 4. j is an integer of 0 or 1. X 1 represents -(CH 2 ) a -(where a is an integer from 1 to 15), -CONH-, -NHCO-, -CO-N(CH 3 )-, -NH-, -O-, -CH 2 O-, -CH 2 -OCO-, -COO- or -OCO-. R 1 represents a fluorine atom, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkoxyalkyl group having 2 to 10 carbon atoms, etc., a monovalent group. In the above formula (V-2), X 2 represents -O-, -CH 2 O-, -CH 2 -OCO-, -COO- or -OCO-. In m, n, X 1 , R 1 When there are 2, each independently has the above definition.

[0164] When using other diamines in addition to the above diamine (0), the amount of the above other diamine is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, based on all the diamine components used to produce the polymer (P).

[0165] (Tetracarboxylic acid component)

[0166] When producing the above polyamic acid (P'), as the tetracarboxylic acid component that reacts with the diamine component, not only tetracarboxylic dianhydride can be used, but also derivatives of tetracarboxylic dianhydride such as tetracarboxylic acid, tetracarboxylic diacyl halide, tetraalkyl ester of tetracarboxylic acid or tetraalkyl ester diacyl halide of tetracarboxylic acid can be used.

[0167] Examples of the above tetracarboxylic dianhydride or its derivatives include acyclic aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride or their derivatives. Among them, tetracarboxylic dianhydride or their derivatives containing at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring and a cyclohexane ring are more preferably included. In particular, tetracarboxylic dianhydride or their derivatives containing at least one structure selected from the group consisting of a cyclobutane ring, a cyclopentane ring and a cyclohexane ring are further preferably included.

[0168] As the tetracarboxylic acid component that can be used to produce the above polyamic acid (P'), the following tetracarboxylic dianhydride or its derivatives (in the present invention, they are also collectively referred to as specific tetracarboxylic derivatives) are preferably included.

[0169] Acyclic aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride; cycloaliphatic tetracarboxylic dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3’,4,4’-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)tetralin-1,2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride; aromatic tetracarboxylic dianhydrides such as 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(3,4-dicarboxyphenoxy)-2,2-diphenylpropane dianhydride, ethylene glycol bisanhydrotrimellitate, 4,4’-(hexafluoroisopropylidene)diphthalic anhydride, 4,4’-carbonyldiphthalic anhydride, 4,4’-oxydi(1,4-phenylenedioxy)bis(phthalic anhydride) or 4,4’-methylenedi(1,4-phenylenedimethylene)bis(phthalic anhydride); and tetracarboxylic dianhydrides described in Japanese Patent Laid-Open No. 2010-97188, etc.

[0170] As preferred examples of the above-mentioned specific tetracarboxylic acid derivatives, there may be mentioned 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-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'-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 or their derivatives.

[0171] The use ratio of the above-mentioned specific tetracarboxylic acid derivative is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 50 mol% or more based on all the tetracarboxylic acid components used.

[0172] Regarding the content ratio of the component (A) and the polymer as the component (B) in the liquid crystal aligning agent of the present invention, the mass ratio of the component (A): the component (B) is preferably 1:99 to 50:50, more preferably 5:95 to 30:70, and further preferably 10:90 to 20:80.

[0173] <(C) component>

[0174] When the liquid crystal aligning agent used in the present invention satisfies the condition Z2, a crosslinking agent is contained as the component (C). As the component (C), there may be mentioned a crosslinking agent having two or more thermally crosslinkable groups B.

[0175] Examples of the crosslinking agent belonging to the component (C) include low molecular weight compounds such as epoxy compounds, compounds having two or more amino groups, hydroxymethyl compounds, isocyanate compounds, phenolic plastic compounds, blocked isocyanate compounds; polymers such as polymers of N-alkoxymethacrylamide, polymers of compounds having an epoxy group, and polymers of compounds having an isocyanate group.

[0176] Specific examples of the above epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane.

[0177] Examples of the compounds having two or more amino groups include diamines such as alicyclic diamines, aromatic diamines, aromatic-aliphatic diamines, and aliphatic diamines.

[0178] Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl dicyclohexylamine, and isophorone diamine.

[0179] 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.

[0180] Examples of the 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-aminobutyl)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, etc.

[0181] Examples of the 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, 1,9-diamino-5-methylnonane, etc.

[0182] Specific examples of the hydroxymethyl compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

[0183] As specific examples of alkoxymethylated glycoluril, for example, 1,3,4,6-tetra(methoxymethyl)glycoluril, 1,3,4,6-tetra(butoxymethyl)glycoluril, 1,3,4,6-tetra(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetra(butoxymethyl)urea, 1,1,3,3-tetra(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone and the like can be cited. As commercially available products, for example, glycoluril compounds manufactured by Mitsui SAITECH Corporation (trade name: CYMEL (registered trademark) 1170, POWDERLINK (registered trademark) 1174), etc., methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin manufactured by DIC Corporation (highly condensed type, trade name: BECKAMINE (registered trademark) J-300S, BECKAMINE P-955, BECKAMINE N), etc. can be cited.

[0184] As specific examples of alkoxymethylated benzoguanamine, for example, tetramethoxymethylbenzoguanamine and the like can be cited. As commercially available products, for example, those manufactured by allnex (trade name: CYMEL (registered trademark) 1123), those manufactured by Sanwa Chemical Co., Ltd. (trade name: NIKALAC (registered trademark) BX-4000, NIKALAC BX-37, NIKALAC BL-60, NIKALAC BX-55H), etc. can be cited.

[0185] As specific examples of alkoxymethylated melamine, for example, hexamethoxymethyl melamine can be cited. As commercially available products, methoxymethyl type melamine compounds manufactured by allnex (trade names: CYMEL (registered trademark) 300, CYMEL 301, CYMEL 303, CYMEL 350), butoxymethyl type melamine compounds (trade names: MICOAT (registered trademark) 506, MICOAT 508), methoxymethyl type melamine compounds manufactured by Sanwa Chemical Co., Ltd. (trade names: NIKALAC (registered trademark) MW-30, NIKALAC MW-22, NIKALAC MW-11, NIKALAC MS-001, NIKALAC MX-002, NIKALAC MX-730, NIKALAC MX-750, NIKALAC MX-035), butoxymethyl type melamine compounds (trade names: NIKALAC (registered trademark) MX-45, NIKALAC MX-410, NIKALAC MX-302), etc. can be cited.

[0186] In addition, it can be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which a hydrogen atom of such an amino group is substituted with a hydroxymethyl group or an alkoxymethyl group. For example, a high molecular weight compound manufactured from a melamine compound and a benzoguanamine compound described in U.S. Patent No. 6323310 can be cited. As a commercially available product of the aforementioned melamine compound, a product with the trade name CYMEL (registered trademark) 303 (manufactured by allnex) etc. can be cited, and as a commercially available product of the aforementioned benzoguanamine compound, a product with the trade name CYMEL (registered trademark) 1123 (manufactured by allnex) etc. can be cited.

[0187] As specific examples of the isocyanate compound, for example, VESTANAT B1358 / 100, VESTAGON BF1540 (the above are isocyanurate type modified polyisocyanates, manufactured by Evonik Japan Co., Ltd.), TAKENATE (registered trademark) B-882N, TAKENATE B-7075 (the above are isocyanurate type modified polyisocyanates, manufactured by Mitsui Chemicals, Inc.), etc. can be cited.

[0188] As specific examples of the phenolic plastic compound, the following compounds can be cited, but the phenolic plastic compound is not limited to the following compound examples.

[0189]

[0190] As specific examples of the compound having two or more hydroxyalkylamide groups at the terminal of the aforementioned molecule, the following compounds, Primid (registered trademark) QM-1260, Primid SF-4510 (the above are manufactured by EMS-CHEMIE) can be cited.

[0191]

[0192] As the blocked isocyanate compound, for example, CORONATE AP STABLE M, CORONATE2503, 2515, 2507, 2513, 2555, MILLIONATE MS-50 (the above are manufactured by Tosoh Corporation), TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (the above are manufactured by Mitsui Chemicals, Inc.) etc. can be cited.

[0193] In addition, as the polymer of the above N-alkoxymethylacrylamide, for example, polymers manufactured using acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl or alkoxymethyl such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide etc. can be cited.

[0194] As specific examples of such polymers, for example, 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. can be cited. The weight average molecular weight of this polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and further preferably 3,000 to 50,000.

[0195] As the polymer of the compound having an epoxy group, for example, polymers manufactured using compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate etc. can be cited.

[0196] As specific examples of such a polymer, for example, 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. can be mentioned. The weight-average molecular weight of this polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.

[0197] As polymers of the above compound having an isocyanate group, for example, polymers produced using a compound having an isocyanate group such as 2-isocyanatoethyl methacrylate (Karenz MOI [registered trademark], manufactured by Showa Denko K.K.), 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]carboxylamino)ethyl methacrylate (Karenz MOI-BM [registered trademark], manufactured by Showa Denko K.K.), 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP [registered trademark], manufactured by Showa Denko K.K.) can be mentioned.

[0198] As specific examples of such a polymer, for example, poly(2-isocyanatoethyl acrylate), poly(2-(0-[1'-methylpropylideneamino]carboxylamino)ethyl methacrylate), a copolymer of 2-isocyanatoethyl methacrylate and styrene, a copolymer of 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate and methyl methacrylate, etc. can be mentioned. The weight-average molecular weight of this polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.

[0199] These crosslinking agents can be used alone or in combination of two or more.

[0200] Regarding the content of the crosslinking agent containing the component (C) in the liquid crystal aligning agent used in the present invention, based on 100 parts by mass of the component (A), it is preferably 1 to 100 parts by mass, more preferably 1 to 80 parts by mass.

[0201] [Preparation of liquid crystal aligning agent]

[0202] The liquid crystal aligning agent used in the present invention is preferably prepared in the form of a coating solution so as to be suitable for forming a liquid crystal alignment film. That is, the liquid crystal aligning agent of the present invention is preferably prepared in the form of a solution obtained by dissolving a resin component for forming a resin coating film in an organic solvent. Here, the resin component refers to the polymer or low molecular compound as the component (A) described above, the polymer as the component (B), and the crosslinking agent as the component (C) as required. At this time, the total content of the component (A), the content of the polymer as the component (B), and the content of the crosslinking agent as the component (C) is preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, still more preferably 1 to 15% by mass, and particularly preferably 1 to 10% by mass with respect to the whole liquid crystal aligning agent.

[0203] <Solvent>

[0204] Regarding the solvent contained in the liquid crystal aligning agent used in the present invention, there is no particular limitation as long as it is a solvent that dissolves the component (A), the component (B), and the component (C) as required. The solvent contained in the liquid crystal aligning agent may be one kind, or two or more kinds may be used in combination. In addition, even if it is not a solvent that dissolves the component (A) and the component (B), it may be used in combination with a solvent that dissolves the component (A) and the component (B). At this time, if the surface energy of the solvent that does not dissolve the component (A) and the component (B) is less than that of the solvent that dissolves the component (A) and the component (B), the coatability of the liquid crystal aligning agent on the substrate can be improved, so it is preferred.

[0205] As specific examples, water, N-alkyl-2-pyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone; dialkylimidazolidinones such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylcaprolactam, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-2-imidazolidinone; lactones such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone; carbonates such as ethylene carbonate and propylene carbonate; ketones such as methanol, ethanol, propanol, isopropanol, 3-methyl-3-methoxybutanol, ethyl pentyl ketone, methyl nonyl ketone, methyl ethyl ketone, isopentyl methyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, 4-hydroxy-4-methyl-2-pentanone; the compound represented by the following formula (Sv-1) and the compound represented by the following formula (Sv-2), 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, isopentyl butyrate, diisobutyl carbitol, diisopentyl ether, etc.

[0206]

[0207] 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, X 1 is an oxygen atom or -COO-, X 2 is a single bond or a carbonyl group, R 1 is an alkylene group having 2 to 4 carbon atoms. n 1 is an integer from 1 to 3. When n 1 is 2 or 3, multiple Rs 1 may be the same or different. Z 1 is a divalent hydrocarbon group having 1 to 6 carbon atoms, Y 3 and Y 4 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

[0208] In formula (Sv-1), as the monovalent hydrocarbon groups having 1 to 6 carbon atoms for Y 1 and Y 2 , examples include monovalent chain hydrocarbon groups having 1 to 6 carbon atoms, monovalent alicyclic hydrocarbon groups having 1 to 6 carbon atoms, and monovalent aromatic hydrocarbon groups having 1 to 6 carbon atoms, etc. As the monovalent chain hydrocarbon groups having 1 to 6 carbon atoms, examples include alkyl groups having 1 to 6 carbon atoms, etc. The alkylene group of R 1 may be linear or branched.

[0209] In formula (Sv-2), as the divalent hydrocarbon group having 1 to 6 carbon atoms for Z 1 , examples include alkylene groups having 1 to 6 carbon atoms, etc.

[0210] As the monovalent hydrocarbon groups having 1 to 6 carbon atoms for Y 3 and Y 4 , examples include monovalent chain hydrocarbon groups having 1 to 6 carbon atoms, monovalent alicyclic hydrocarbon groups having 1 to 6 carbon atoms, and monovalent aromatic hydrocarbon groups having 1 to 6 carbon atoms, etc. As the monovalent chain hydrocarbon groups having 1 to 6 carbon atoms, examples include alkyl groups having 1 to 6 carbon atoms, etc.

[0211] Specific examples of the solvent represented by formula (Sv-1) include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, propylene glycol diacetate, ethylene glycol, 1,4-butanediol, 3-methoxybutyl acetate, 3-ethoxybutyl acetate, etc.;

[0212] Specific examples of the solvent represented by (Sv-2) include, for example, methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, etc.

[0213] As the aforementioned solvent, the boiling point is preferably in the range 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 pentyl ketone, methyl ethyl ketone, isoamyl methyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, 4-hydroxy-4-methyl-2-pentanone, 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, isoamyl butyrate, diisobutyl carbitol, diisopentyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutyl acetate, methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, etc.

[0214] Particularly when the liquid crystal aligning agent containing the aforementioned solvent is coated on the plastic substrate described below, a boiling point in this range is preferred.

[0215] <Other components>

[0216] The liquid crystal aligning agent used in the present invention may contain other components in addition to the above components (A), (B), and, if necessary, the above component (C). Examples of such other components include crosslinking catalysts, compounds that improve the film thickness uniformity and / or surface smoothness when the liquid crystal aligning agent is coated, compounds that improve the adhesion between the liquid crystal alignment film and the substrate, etc., but are not limited thereto.

[0217] <Crosslinking catalyst>

[0218] In the liquid crystal aligning agent used in the present invention, a crosslinking catalyst may be added for the purpose of promoting the reaction between the thermally crosslinkable group A and the thermally crosslinkable group B. Examples of such crosslinking catalysts 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, dodecylbenzenesulfonic acid, etc., or their hydrates, salts, etc. Examples of compounds that generate acid upon heating include, for example, bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylene tris(methylsulfonate), pyridinium p-toluenesulfonate, morpholinium p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl p-toluenesulfonamide, etc.

[0219] [Compound for improving film thickness uniformity and surface smoothness]

[0220] Examples of compounds that improve the film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.

[0221] Specifically, for example, Eftop (registered trademark) 301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.), Megafac (registered trademark) F171, F173, R-30 (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited), AsahiGuard (registered trademark) AG710 (manufactured by AGC Inc.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC SEIMI CHEMICAL Co., Ltd.), etc.

[0222] The usage ratio of these surfactants is preferably 0.01 part by mass to 2 parts by mass, more preferably 0.01 part by mass to 1 part by mass, relative to 100 parts by mass of the resin component contained in the polymer composition.

[0223] [Compound for improving the adhesion between the liquid crystal alignment film and the substrate]

[0224] As specific examples of the compound for improving the adhesion between the liquid crystal alignment film and the substrate, compounds containing functional silanes as shown below can be cited.

[0225] 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-triethoxysilylpropyltriethylenetetramine, N-3-trimethoxysilylpropyltriethylenetetramine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diaza-nonyl acetate, 9-triethoxysilyl-3,6-diaza-nonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and other compounds containing amino-based silanes.

[0226] When using the compound for improving the adhesion to the substrate, its usage amount is preferably 0.1 part by mass to 30 parts by mass, more preferably 1 part by mass to 20 parts by mass, relative to 100 parts by mass of the resin component contained in the polymer composition.

[0227] In a certain embodiment, in order to improve the photoreactivity of the photo-orienting group, a photosensitizer can also be used as an additive. As specific examples, aromatic 2-hydroxyketones (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthenone, thioxanthone, and acetophenone ketal can be cited.

[0228] [Liquid crystal alignment film and liquid crystal display element]

[0229] The liquid crystal aligning agent of the present invention can be made into a liquid crystal alignment film by coating on a substrate, firing, and then performing alignment treatment such as rubbing treatment or light irradiation, or can be made into a liquid crystal alignment film without alignment treatment in some applications such as vertical alignment. As the substrate, for example, glass such as float glass and soda-lime glass can be used; a transparent substrate formed 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 cellulose triacetate can be used.

[0230] As the transparent conductive film provided on one side of the substrate, a NESA film (registered trademark of PPG Industries, Inc. in the United States) containing tin oxide (SnO 2 ), an ITO film containing indium oxide - tin oxide (In 2 O 3 -SnO 2 ) etc. can be used.

[0231] <Coating film forming step>

[0232] The coating method of the liquid crystal aligning agent of the present invention is not particularly limited, and there are screen printing, flexographic printing, offset printing, inkjet, dip coating, roll coating, slot coating, spin coating, etc., and they can be used according to the purpose. After coating on the substrate by these methods, the solvent is evaporated by heating means such as a hot plate, and thus a coating film can be formed.

[0233] The firing after coating the liquid crystal aligning agent can be carried out at any temperature from 40 to 300 °C, preferably from 40 °C to 250 °C, more preferably from 40 °C to 230 °C.

[0234] The film thickness of the coating film formed on the substrate is preferably 5 to 1,000 nm, more preferably 10 to 500 nm or 10 to 300 nm. This firing can be carried out using a hot plate, a hot air circulation furnace, an infrared furnace, etc.

[0235] For the rubbing treatment, rayon cloth, nylon cloth, cotton cloth, etc. can be used.

[0236] <Light irradiation step>

[0237] In one embodiment, the alignment treatment can be carried out by light irradiation, and it can include, for example, the following steps: a step of coating the above liquid crystal aligning agent on a substrate and forming a coating film; and a step of irradiating the above coating film in a state where the coating film does not contact the liquid crystal layer or in a state where the coating film contacts the liquid crystal layer.

[0238] As the light irradiated in the alignment treatment based on light irradiation, for example, ultraviolet rays including light having a wavelength of 150 to 800 nm, visible light, etc. can be cited. Among these, ultraviolet rays including light having a wavelength of 300 to 400 nm are preferred. The irradiated light may be polarized light or non-polarized light. As the polarized light, light including linearly polarized light is preferably used.

[0239] When the light used is polarized light, the light can be irradiated from a direction perpendicular to the substrate surface, from an inclined direction, or they can be combined. When irradiating non-polarized light, it is preferably performed from an inclined direction with respect to the substrate surface.

[0240] The irradiation amount of light is preferably set to 0.1 mJ / cm 2 or more and less than 1,000 mJ / cm 2 , more preferably set to 1 to 500 mJ / cm 2 , further preferably set to 2 to 200 mJ / cm 2 .

[0241] <Liquid crystal display element>

[0242] The liquid crystal display element of the present invention is a vertically aligned liquid crystal display element, which includes: a liquid crystal cell having two substrates arranged oppositely, a liquid crystal layer provided between the substrates, and a liquid crystal alignment film provided between the substrate and the liquid crystal layer and formed of the liquid crystal aligning agent of the present invention. Specifically, the liquid crystal cell of such a vertically aligned liquid crystal display element is fabricated as follows: The liquid crystal aligning agent of the present invention is coated on the two substrates and fired to form a liquid crystal alignment film, the two substrates are arranged with the liquid crystal alignment films facing each other, a liquid crystal layer composed of liquid crystal is sandwiched between the two substrates, and a liquid crystal cell is fabricated by irradiating ultraviolet rays.

[0243] In this way, it can be considered that: by using the liquid crystal alignment film formed of the liquid crystal aligning agent of the present invention and irradiating the liquid crystal alignment film and the liquid crystal layer with ultraviolet rays, an interaction occurs between the liquid crystal and the liquid crystal alignment film of the present invention, thereby forming a liquid crystal display element with a small residual DC of the liquid crystal and less prone to image sticking.

[0244] As the substrate used in the liquid crystal display element of the present invention, as long as it is a substrate with high transparency, there is no particular limitation, and it is usually a substrate on which a transparent electrode for driving the liquid crystal is formed. As a specific example, the same substrates as those described in the above liquid crystal alignment film can be cited.

[0245] The liquid crystal display element of the present invention can use a substrate provided with an existing electrode pattern and a protrusion pattern, or can also be operated using a substrate having the following structure: a structure in which a line / slit electrode pattern of 1 to 10 μm is formed on one side substrate through a liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention, and no slit pattern or protrusion pattern is formed on the opposing substrate. It is possible to simplify the process during element manufacturing and obtain a high transmittance.

[0246] In addition, in a high-functional element such as a TFT type element, those in which an element such as a transistor is formed between the electrode for liquid crystal driving and the substrate can be used.

[0247] In the case of a transmissive liquid crystal display element, the above substrate is usually used, but in a reflective liquid crystal display element, not only a single-sided substrate can be used, but also an opaque substrate such as a silicon wafer can be used. At this time, for the electrode formed on the substrate, a material such as aluminum that reflects light can also be used.

[0248] The liquid crystal alignment film is formed by coating the liquid crystal aligning agent of the present invention on the substrate and then firing, as described above in detail.

[0249] As the liquid crystal composition used in the liquid crystal display element of the present invention, a nematic liquid crystal having a negative dielectric anisotropy can be used. 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, terphenyl-based liquid crystals, etc. can be used. In addition, an alkenyl-based liquid crystal is preferably used in combination. As such an alkenyl-based liquid crystal, conventionally known liquid crystals can be used. For example, compounds represented by the following formulas can be cited, but are not limited thereto.

[0250]

[0251] 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 the vertical alignment mode. For example, liquid crystal compositions having a negative dielectric anisotropy manufactured by Merck & Co., Inc., such as MLC-6608 and MLC-6609, can be used. Furthermore, MLC-3022 and MLC-3023 (including a photopolymerizable compound (RM)) manufactured by Merck & Co., Inc., which are liquid crystal compositions containing an alkenyl-based liquid crystal and having a negative dielectric anisotropy, can be used.

[0252] As a method of sandwiching the liquid crystal layer between two substrates, known methods can be cited. For example, the following method can be cited: Prepare a pair of substrates on which a liquid crystal alignment film is formed, scatter spacers such as beads on the liquid crystal alignment film of one substrate, apply an adhesive around the substrate, and then paste the other substrate with the side having the liquid crystal alignment film facing inward, inject the liquid crystal under reduced pressure and seal it.

[0253] In addition, a liquid crystal cell can be fabricated by the following method: Prepare a pair of substrates each having a liquid crystal alignment film formed thereon. After dispersing spacers such as beads on the liquid crystal alignment film of one substrate, a liquid crystal is dropped thereon. Thereafter, the side having the liquid crystal alignment film formed thereon is made the inner side, and the other substrate is pasted and sealed. The thickness of the spacers at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm.

[0254] The step of fabricating the liquid crystal cell by irradiating the liquid crystal alignment film and the liquid crystal layer with ultraviolet rays can be at any time as long as it is after the liquid crystal is enclosed. The irradiation amount of the ultraviolet rays is, for example, 1 to 60 J / cm 2 and preferably 40 J / cm 2 Hereinafter, when the irradiation amount of the ultraviolet rays is small, a reduction in reliability due to damage to the components constituting the liquid crystal display element can be suppressed.

[0255] The wavelength of the ultraviolet rays used is preferably 300 to 500 nm, more preferably 300 to 400 nm. It should be noted that the wavelength of the ultraviolet rays used in the step of fabricating the liquid crystal cell is preferably different from the wavelength of the ultraviolet rays used in the aforementioned light irradiation step. Among them, from the viewpoint of preventing the reverse reaction in the light irradiation step in the step of fabricating the liquid crystal cell from being aggravated, it is preferable that the wavelength of the ultraviolet rays used in the step of fabricating the liquid crystal cell is longer than the wavelength of the ultraviolet rays used in the aforementioned light irradiation step.

[0256] For example, it is preferable that: the wavelength of the ultraviolet rays used in the aforementioned light irradiation step is 300 to 350 nm, and the wavelength of the ultraviolet rays used in the step of fabricating the liquid crystal cell is 350 to 400 nm. By operating in this way, in the PSA treatment after the photoalignment treatment, a problem that the reverse reaction of the photoalignment groups is aggravated to impair the photoalignment property can be avoided.

[0257] In addition, the ultraviolet ray irradiation on the liquid crystal alignment film and the liquid crystal layer can be performed under the condition that a voltage is applied and this electric field is maintained. Here, as the voltage applied between the electrodes, it is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p.

[0258] In the case of the PSA method in which a polymerizable compound is contained in the liquid crystal, when the liquid crystal alignment film and the liquid crystal layer are irradiated with ultraviolet rays, the polymerizable compound reacts to form a polymer, and the tilt direction of the liquid crystal molecules is memorized by this polymer. Thereby, the response speed of the obtained liquid crystal display element can be increased.

[0259] The liquid crystal aligning agent of the present invention undergoes a photoreaction through the photoalignment group of the polymer or low molecular compound as the (A) component through the above-mentioned photoalignment process, thereby imparting a tilt angle. Thereafter, when the PSA treatment is performed, free radicals are generated from the alkenyl liquid crystal in the liquid crystal composition and polymerized, thereby enabling the imparted tilt angle to be fixed. Thus, the durability of the tilt angle of the obtained liquid crystal display element can be improved.

[0260] The liquid crystal aligning agent is useful not only as a liquid crystal aligning agent for producing a vertically aligned liquid crystal display element such as a PSA type liquid crystal display and a SC-PVA type liquid crystal display, but can also be suitably used for producing a liquid crystal aligning film formed by a rubbing treatment or a photo-alignment treatment.

[0261] Example

[0262] The present invention is described in more detail below with reference to Examples, but the present invention is not to be construed as being limitative thereof. The abbreviations of the compounds used and the methods for measuring the properties are as follows.

[0263] (Organic Solvent)

[0264] NMP: N-methyl-2-pyrrolidone

[0265] BCS: Ethylene glycol monobutyl ether

[0266] THF: Tetrahydrofuran (tetracarboxylic dianhydride)

[0267] CA-1 to CA-2: compounds represented by the following formulae (CA-1) to (CA-2), respectively (diamines)

[0268] DA-1 to DA-7: compounds represented by the following formulae (DA-1) to (DA-7), respectively (acrylic monomers)

[0269] MA-1 to MA-3: compounds represented by the following formulas (MA-1) to (MA-3), respectively (initiators)

[0270] IN-1: Compound represented by the following formula (IN-1) (reaction reagent)

[0271] DMAP: N,N-dimethyl-4-aminopyridine

[0272] EDC: 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride

[0273]

[0274] <Measurement of Viscosity>

[0275] Using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL and a conical rotor TE-1 (1°34’, R24), the measurement was carried out at a temperature of 25°C.

[0276] <Measurement of molecular weight>

[0277] The measurement was carried out using the following room temperature GPC (gel permeation chromatography) apparatus, and Mn and Mw were calculated in the form of polyethylene glycol and polyethylene oxide conversion values.

[0278] GPC apparatus: GPC-101 (manufactured by Showa Denko K.K.); Column: Series connection of GPC KD-803 and GPC KD-805 (manufactured by Showa Denko K.K.); Column temperature: 50°C; Eluent: N,N-dimethylformamide (as additives, lithium bromide monohydrate (LiBr·H 2 O) is 30 mmol / L, phosphoric acid·anhydrous crystal (orthophosphoric acid) is 30 mmol / L, and tetrahydrofuran (THF) is 10 mL / L), Flow rate: 1.0 mL / min

[0279] Standard samples for making the standard curve: TSK standard polyethylene oxide (molecular weights: approximately 900,000, 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 Laboratories).

[0280] [Synthesis of specific diamines (DA-1) to (DA-3)]

[0281] The synthesis methods of the compounds represented by formulas (DA-1) to (DA-3) are described in detail below. It should be noted that the compounds represented by formulas (DA-1) to (DA-3) are novel compounds not disclosed in the literature, etc.

[0282] < 1 <Measurement of 1H-NMR>

[0283] Apparatus: Fourier transform superconducting nuclear magnetic resonance apparatus (FT-NMR) "AVANCE III" (manufactured by BRUKER), 500 MHz.

[0284] Solvent: Deuterated dimethyl sulfoxide ([D 6 -DMSO, Standard substance: Tetramethylsilane).

[0285] <Monomer synthesis example 1: Synthesis of (DA-1)>[[]]

[0286] The diamine (DA-1) was synthesized according to the route shown below.

[0287]

[0288] In a flask, to 3,5-dinitrobenzoic acid (42.4 g, 200 mmol), THF (296 g), cyclododecanol (36.8 g, 200 mmol), DMAP (2.44 g, 20.0 mmol) and EDC (37.3 g, 195 mmol) were added, and the reaction was carried out for 18 hours under a nitrogen atmosphere at room temperature. After the reaction was completed, the insoluble matter was removed by filtration, and then the reaction solution was poured into pure water to obtain the crude product of the reactant. The obtained crude product was slurried and washed with pure water / methanol (50 / 50 (vol% / vol%)), thereby obtaining DA-1-1 (55.9 g, 148 mmol, yield 74%, white solid).

[0289]

[0290] In a flask, to DA-1-1 (55.9 g, 148 mmol), THF (449 g) and palladium supported on carbon (5% Pd carbon powder (50% water-containing product) K type, manufactured by N.E. CHEMCAT Corporation) (4.47 g) were added, and nitro reduction was carried out under a hydrogen atmosphere at room temperature. After the reaction, the palladium supported on carbon was removed by filtration, and then the filtrate was concentrated, thereby obtaining DA-1 (45.3 g, 142 mmol, yield 96%, white solid).

[0291] According to the results of 1 1H-NMR shown below, it was confirmed that this solid was diamine (DA-1).

[0292] 1 1H-NMR (500 MHz, [D 6 -DMSO): δ (ppm =) 6.41 (d, 2H, J = 2.0 Hz), 6.01 (t, 1H, J = 2.0 Hz), 5.07 (q, 1H, J = 5.8 Hz), 4.97 (s, 4H), 1.75 - 1.35 (m, 22H).

[0293] <Synthesis Example 2 of Monomer: Synthesis of (DA-2)>

[0294] Diamine (DA-2) was synthesized according to the route shown below.

[0295]

[0296] In a flask, to 1,3-dinitrobenzoic acid (42.4 g, 200 mmol), THF (200 g), cyclooctanol (25.6 g, 200 mmol), DMAP (2.44 g, 20.0 mmol) and EDC (37.3 g, 195 mmol) were added, and the reaction was carried out for 18 hours under a nitrogen atmosphere at room temperature. After the reaction was completed, the insoluble matter was removed by filtration, and then the reaction solution was poured into pure water to obtain the crude product of the reactant. The obtained crude product was slurried and washed with pure water / methanol (50 / 50 (vol% / vol%)), thereby obtaining DA-2-1 (41.7 g, 129 mmol, yield 65%, white solid).

[0297]

[0298] In a flask, to DA-2-1 (41.7 g, 129 mmol), THF (335 g) and palladium supported on carbon (5% Pd carbon powder (50% water-containing product) K type, manufactured by N.E.CHEMCAT Corporation) (3.34 g) were added, and nitro reduction was carried out under a hydrogen atmosphere at room temperature. After the reaction, the palladium supported on carbon was removed by filtration, and then the filtrate was concentrated, thereby obtaining DA-2 (31.9 g, 122 mmol, yield 94%, white solid).

[0299] According to the results of 1 1H-NMR shown below, it was confirmed that this solid was diamine (DA-2).

[0300] 1 1H-NMR (500 MHz, [D 6 -DMSO): δ (ppm =) 6.41 (d, 2H, J = 2.0 Hz), 6.01 (t, 1H, J = 2.0 Hz), 4.96 (s, 4H), 5.01 - 4.94 (m, 1H), 1.84 - 1.51 (m, 14H).

[0301] <Synthesis Example of Monomer 3: Synthesis of (DA-3)>

[0302] According to the route shown below, diamine (DA-3) was synthesized.

[0303]

[0304] In a flask, for 3,5-dinitrobenzoic acid (5.74 g, 27.0 mmol), THF (48.0 g), cyclopentadecanol (6.10 g, 26.9 mmol), DMAP (0.328 g, 2.68 mmol), and EDC (5.01 g, 26.1 mmol) were added, and the reaction was carried out for 18 hours under a nitrogen atmosphere at room temperature. After the reaction was completed, the insoluble matter was removed by filtration, and the reaction solution was poured into pure water to obtain a crude product of the reactant. The obtained crude product was slurried and washed with pure water / methanol (50 / 50 (vol% / vol%)), whereby DA-3-1 (6.72 g, 16.0 mmol, yield 59%, white solid) was obtained.

[0305]

[0306] In a flask, for DA-3-1 (6.72 g, 16.0 mmol), THF (53.8 g) and palladium supported on carbon (5% Pd carbon powder (50% water-containing product) K type, manufactured by N.E.CHEMCAT Corporation) (0.538 g) were added, and nitro reduction was carried out under a hydrogen atmosphere at room temperature. After the reaction, the palladium supported on carbon was removed by filtration, and the filtrate was concentrated, whereby DA-3 (5.49 g, 15.2 mmol, yield 95%, white solid) was obtained.

[0307] According to the results of 1 1H-NMR shown below, it was confirmed that this solid was diamine (DA-3).

[0308] 1 1H-NMR (500 MHz, [D 6 -DMSO): δ (ppm =) 6.41 (d, 2H, J = 2.0 Hz), 6.01 (t, 1H, J = 2.0 Hz), 4.97 (s, 4H), 4.98 - 4.95 (m, 1H), 1.68 - 1.33 (m, 28H).

[0309] [Synthesis of Polymer]

[0310] [Synthesis Example 1]

[0311] DA-1 (4.78 g, 15.0 mmol) and NMP (21.8 g) were added to a 50 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and the mixture was stirred at room temperature for 0.5 hour while introducing nitrogen. Thereafter, CA-1 (2.91 g, 14.8 mmol) and NMP (13.3 g) were added, and the mixture was stirred at 40 °C for 3 hours, whereby a polyamic acid solution (1) having a solid component concentration of 18% by mass was obtained. The Mn of this polyamic acid was 11,500 and the Mw was 28,700.

[0312] <Synthesis Example 2>

[0313] DA-2 (3.94 g, 15.0 mmol) and NMP (17.9 g) were added to a 50 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and the mixture was stirred at room temperature for 0.5 hour while introducing nitrogen. Thereafter, CA-1 (2.91 g, 14.8 mmol) and NMP (13.3 g) were added, and the mixture was stirred at 40 °C for 3 hours to obtain a polyamic acid solution (2) with a solid component concentration of 18% by mass. The Mn of this polyamic acid was 13,500 and the Mw was 41,200.

[0314] <Synthesis Example 3>

[0315] DA-3 (5.41 g, 15.0 mmol) and NMP (24.6 g) were added to a 50 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and the mixture was stirred at room temperature for 0.5 hour while introducing nitrogen. Thereafter, CA-1 (2.93 g, 14.9 mmol) and NMP (13.3 g) were added, and the mixture was stirred at 40 °C for 3 hours to obtain a polyamic acid solution (3) with a solid component concentration of 18% by mass. The Mn of this polyamic acid was 10,500 and the Mw was 23,500.

[0316] <Synthesis Example 4>

[0317] DA-4 (1.62 g, 15.0 mmol) and NMP (7.39 g) were added to a 50 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and the mixture was stirred at room temperature for 0.5 hour while introducing nitrogen. Thereafter, CA-1 (2.87 g, 14.6 mmol) and NMP (13.1 g) were added, and the mixture was stirred at 40 °C for 3 hours to obtain a polyamic acid solution (4) with a solid component concentration of 18% by mass. The Mn of this polyamic acid was 11,600 and the Mw was 22,700.

[0318] <Synthesis Example 5>

[0319] DA-5 (0.910 g, 5.98 mmol), DA-6 (1.09 g, 4.50 mmol), DA-1 (1.43 g, 4.49 mmol), CA-2 (0.750 g, 3.00 mmol) and NMP (16.7 g) were added to a 50 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and the mixture was stirred at 60 °C for 3 hours while introducing nitrogen. Thereafter, CA-1 (2.32 g, 11.8 mmol) and NMP (9.30 g) were added, and the mixture was stirred at 40 °C for 3 hours to obtain a polyamic acid solution (5) with a solid component concentration of 20% by mass. The Mn of this polyamic acid was 12,500 and the Mw was 33,600.

[0320] <Synthesis Example 6>

[0321] DA-5 (0.910 g, 5.98 mmol), DA-6 (1.09 g, 4.50 mmol), DA-7 (1.71 g, 4.49 mmol), CA-2 (0.750 g, 3.00 mmol) and NMP (17.9 g) were added to a 50 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and the mixture was stirred at 60 °C for 3 hours while introducing nitrogen. Thereafter, CA-1 (2.33 g, 11.9 mmol) and NMP (9.33 g) were added, and the mixture was stirred at 40 °C for 3 hours to obtain a polyamic acid solution (6) having a solid component concentration of 20% by mass. The Mn of this polyamic acid was 11,500 and the Mw was 30,000.

[0322] <Synthesis Example 7>

[0323] MA-1 (4.56 g, 9.00 mmol), MA-2 (1.07 g, 7.50 mmol), MA-3 (1.16 g, 13.5 mmol) and NMP (38.7 g) were added to a 50 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and the mixture was stirred at room temperature for 0.5 hours while introducing nitrogen. Thereafter, IN-1 (0.0493 g, 0.300 mmol) was added, and the mixture was stirred at 75 °C for 12 hours to obtain a polymethacrylate solution (1) having a solid component concentration of 15% by mass. The Mn of this polymethacrylate was 14,500 and the Mw was 47,600.

[0324] The specifications of the respective polymers obtained in Synthesis Examples 1 to 6 above are shown in Table 1 below.

[0325] [Table 1]

[0326] Table 1.

[0327]

[0328] [Preparation of Liquid Crystal Alignment Agent]

[0329] <Example 1>

[0330] To the polyamic acid solution (1) (2.83 g) obtained in Synthesis Example 1 and the polymethacrylate solution (1) (0.60 g) obtained in Synthesis Example 7, NMP (5.57 g) and BCS (6.00 g) were added, and the mixture was stirred at room temperature for 3 hours to obtain a liquid crystal alignment agent (A-1).

[0331] <Examples 2 and 3, Comparative Example 1>

[0332] Using the polyamic acid solutions (2), (3), and (4) to replace the polyamic acid solution (1), and performing the same operations as in Example 1, the liquid crystal aligning agents (A-2), (A-3), and (B-1) of Example 2, Example 3, and Comparative Example 1 were obtained.

[0333] <Example 4>

[0334] To the polyamic acid solution (5) (2.55 g) obtained by Synthesis Example 5 and the polymethacrylate solution (1) (0.60 g) obtained by Synthesis Example 7, NMP (5.85 g) and BCS (6.00 g) were added, and the mixture was stirred at room temperature for 3 hours to obtain a liquid crystal aligning agent (A-4).

[0335] <Comparative Example 2>

[0336] Using the polyamic acid solution (6) to replace the polyamic acid solution (5), and performing the same operations as in Example 4, the liquid crystal aligning agent (B-2) of Comparative Example 2 was obtained.

[0337] The specifications of the liquid crystal aligning agents obtained in the above Examples and Comparative Examples are shown in Table 2 below.

[0338] [Table 2]

[0339] Table 2.

[0340]

[0341] As described above, no abnormalities such as turbidity and precipitation were observed in the obtained liquid crystal aligning agents (A-1) to (A-4), (B-1) to (B-2), and it was confirmed that they were uniform solutions. Using the obtained liquid crystal aligning agents, the pretilt angle was evaluated.

[0342] [Fabrication of Liquid Crystal Cell]

[0343] Using the liquid crystal aligning agents obtained above, the liquid crystal cell was fabricated according to the steps shown below.

[0344] The liquid crystal aligning agent was spin-coated on a glass substrate with an ITO electrode, dried on a hot plate at 70 °C for 90 seconds, and then fired in an infrared heating furnace at 200 °C for 30 minutes to form a liquid crystal alignment film with a film thickness of 100 nm. Then, through a polarizing plate, linearly polarized ultraviolet light with a wavelength of 313 nm, an irradiation intensity of 4.3 mW / cm 2 , and an irradiation intensity of 50 mJ / cm 2 was irradiated on the coating surface at an angle of 40° from the substrate normal direction to obtain a substrate with a liquid crystal alignment film. The linearly polarized ultraviolet light was prepared by passing the ultraviolet light of a high-pressure mercury lamp through a band-pass filter with a wavelength of 313 nm and then through a polarizing plate with a wavelength of 313 nm.

[0345] Prepare two pieces of the above substrates. After scattering 4-μm bead spacers on the liquid crystal alignment film of one substrate, apply a sealant (manufactured by Mitsui Chemicals, Inc., XN-1500T). Then, paste the other substrate with the liquid crystal alignment film surfaces facing each other and the alignment directions being 180° apart, and heat-cure the sealant at 120°C for 90 minutes to fabricate an empty cell.

[0346] Inject a liquid crystal (manufactured by MERCK, MLC-3022) into the empty cell by the reduced-pressure injection method to obtain a liquid crystal display element.

[0347] (Evaluation of pretilt angle)

[0348] The pretilt angle of the liquid crystal cell is measured using AxoScan manufactured by Axometrics, Inc., and the measurement is performed by the Mueller Matrix method. The evaluation results are shown in Table 3. The lower the value, the better.

[0349] (Evaluation of voltage holding ratio)

[0350] In the measurement of the voltage holding ratio of the liquid crystal cell, use VHR-1 manufactured by TOYO TECHNICA. Apply a 1-V voltage for 60 μs in a hot air circulation oven at 60°C, and then measure the voltage after 1000 msec to calculate to what extent the voltage can be maintained as the voltage holding ratio. The evaluation results are shown in Table 3. When it is 80% or more, it is regarded as good.

[0351] [Table 3]

[0352] Table 3.

[0353]

[0354] From the results in Table 3, it can be seen that the example using the liquid crystal alignment film obtained from a liquid crystal aligning agent whose diamine component contains a specific diamine is different from the comparative example using the liquid crystal alignment film obtained from a liquid crystal aligning agent whose diamine component does not contain the specific diamine, and it shows a pretilt angle of 2° or more from the vertical. In addition, it can be seen that it shows a high voltage holding ratio.< / x> < / x>

Claims

1. A liquid crystal aligning agent comprising a polymer or a low molecular weight compound as component (A), a polymer (P) as component (B), and a solvent, The polymer or low molecular compound has a photo-alignment group and a thermal cross-linking group represented by the following formula (pa-1), wherein A represents a pyrimidine-2,5-diyl group, a pyridine-2,5-diyl group, a thiophene-2,5-diyl group, a furan-2,5-diyl group, a 1,4-naphthylene group or a phenylene group, or a 2,6-naphthylene group or a phenylene group, which is substituted by a group selected from a fluorine atom, a chlorine atom, a cyano group, or an alkoxy group having 1 to 5 carbon atoms, a linear alkyl residue, or a branched alkyl residue, and the alkoxy group having 1 to 5 carbon atoms, a linear alkyl residue, or a branched alkyl residue is substituted by 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, a divalent heterocyclic group or a divalent condensed ring group; R 3 is a single bond, an oxygen atom, -COO- or -OCO-; R 4 is a linear or branched alkyl group having 1 to 40 carbon atoms, or a monovalent organic group having 3 to 40 carbon atoms including an alicyclic group; D represents an oxygen atom, a sulfur atom or -NR d -, where R d represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; a is an integer of 0 to 3; * represents a bonding position; when a is 2 or more, multiple R 1 and R 2 Each independently has the above definition; X and Y are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 3 carbon atoms, wherein a part or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms, The polymer (P) is at least one selected from the group consisting of a polyimide precursor and a polyimide, the polyimide is an imide of the polyimide precursor, and the polyimide precursor is prepared using a polymer having the following formula (D A ) is obtained by using the diamine component of the diamine (0) shown in formula (D A ), X 1 and X 2 Each is independently selected from a single bond, an ether bond, -COO-, -OCO-, -NHCO-, -CONH-, a urethane bond, a urea bond, a thioether bond, -Si(R 1 )(R 2 )-、-Si(R 3 )(R 4 )-O- and -N(R 5 )-, in, R 1 and R 2 Each independently represents an alkyl group having 1 to 3 carbon atoms bonded to Si, R 3 and R 4 Each independently represents an alkyl group having 1 to 3 carbon atoms bonded to Si, R 5 represents a hydrogen atom bonded to N or an alkyl group having 1 to 3 carbon atoms; n is an integer of 1 to 6; Cy represents a non-aromatic cyclic group having 7 to 20 members; R 11 and R 12 Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; wherein X 2 When it is a single bond, n is 0.

2. The liquid crystal alignment agent according to claim 1, further satisfying at least one of the following conditions Z1 and Z2, Z1: The polymer as component (A) has a thermally crosslinkable group A and a thermally crosslinkable group B; Z2: The polymer as the component (A) has a thermally crosslinkable group A, and the component (C) further includes a compound having two or more thermally crosslinkable groups B in the molecule, The heat-crosslinkable group A and the heat-crosslinkable group B are each independently an organic group selected from the group consisting of a carboxyl group, a protected carboxyl group, an amino group, a protected amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, a protected hydroxyl group, an epoxy group, an oxetanyl group, a thiirane group, an isocyanate group, and a blocked isocyanate group, and the heat-crosslinkable group A and the heat-crosslinkable group B are selected so as to cause a crosslinking reaction by heat. in, When both the thermally crosslinkable group A and the thermally crosslinkable group B are self-crosslinkable groups, the thermally crosslinkable group A and the thermally crosslinkable group B are optionally the same as each other.

3. The liquid crystal alignment agent according to claim 1, in, The diamine (0) is selected from the following formula (d A -1)~(d A -3) any diamine in the group consisting of, 4. The liquid crystal alignment agent according to claim 1, in, The polymer (P) is obtained by a polycondensation reaction of the diamine component and a tetracarboxylic acid component, and the tetracarboxylic acid component contains acyclic aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, or a derivative thereof.

5. The liquid crystal alignment agent according to claim 1, in, The amount of the diamine (0) used is 5 mol% or more based on the diamine component. 6 . A liquid crystal aligning film formed using the liquid crystal aligning agent according to claim 1 .

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

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