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

Abstract

To provide a liquid crystal alignment membrane that has small variation in pretilt angle even after long-time driving to have superior reliability on a display, a liquid crystal display element with the same, and a liquid crystal alignment agent imparting the same.SOLUTION: A liquid crystal alignment agent contains: as a component (A), a polymer having an optical alignment group expressed by formula (pa-1), where A represents pyrimidine-2,5-diyl etc., substituted occasionally by a group selected out of fluorine, chlorine and cyano, or a C1-5 alkoxy group or linear or branched alkyl residue, R1 is a single bond, an oxygen atom, -COO-, or -OCO-, R2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocycle group or a divalent condensed ring group, R3 is -COO- or -OCO-, R4 is a C3-40 univalent organic group including a C1-40 linear or branched alkyl group or alicyclic group, and D is an oxygen atom, a sulfur atom, or -NRd-); and a solvent.SELECTED DRAWING: None

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

[0002] In liquid crystal display elements, the role of liquid crystal alignment films is to align liquid crystals in a specific direction. Currently, the main liquid crystal alignment films used industrially are made by applying a polyimide-based liquid crystal alignment agent made from a polyimide precursor, polyamic acid (also called polyamic acid), polyamic acid ester, or polyimide solution, to a substrate and forming a film. Furthermore, when the liquid crystal is to be aligned parallel or tilted to the substrate surface, a surface stretching treatment by rubbing is further carried out after the film formation.

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

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

[0005] VA-mode liquid crystal display elements are used in TVs and in-vehicle displays due to their high contrast and wide viewing angle. TV LCD elements use backlights that generate a large amount of heat to achieve high brightness, while LCD elements used in in-vehicle applications, such as car navigation systems and instrument panels, are often used or left in high-temperature environments for long periods of time. Under such harsh conditions, gradual changes in the pretilt angle can lead to problems such as loss of initial display characteristics and display unevenness. Furthermore, the voltage retention and charge storage characteristics of the liquid crystal are also affected by the liquid crystal alignment film. A low voltage retention ratio leads to reduced display contrast, while a high charge storage rate relative to the DC voltage can cause image burn-in. To increase transmittance, a relatively large tilt angle of more than 2° from the vertical is particularly required. However, no materials capable of imparting such a large tilt angle through photo-alignment treatment and stably maintaining the imposed tilt angle have been available. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 3-179323 [Patent Document 2] Japanese Patent Application Publication No. 4-281427 [Patent Document 3] Patent No. 4504626 [Patent Document 4] Patent No. 4995267 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal alignment film which has little change in pretilt angle even after long-term driving, excellent display reliability, high voltage retention characteristics, and reduced charge accumulation; a liquid crystal display element having the same; and a liquid crystal aligning agent for providing the same. [Means for solving the problem]

[0008] The present inventors have <x>The present inventors have discovered the invention as summarized below. <x>As the component (A), pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4 ... - or 2,6-naphthylene or phenylene, R1 is a single bond, an oxygen atom, -COO- or -OCO-, R2 is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group or a divalent fused ring group, R3 is -COO- or -OCO-, R4 is a monovalent organic group having 3 to 40 carbon atoms containing a linear or branched alkyl group or an alicyclic group having 1 to 40 carbon atoms, D is an oxygen atom, a sulfur atom or -NR d -(where R d represents a hydrogen atom or an alkyl having 1 to 3 carbon atoms, a is an integer of 0 to 3, and * represents a bonding position. A liquid crystal aligning agent comprising a polymer having a photoalignable group represented by (), and a solvent.

[0009] [ka] [Effects of the Invention]

[0010] The present invention provides a liquid crystal alignment film and a liquid crystal aligning agent that have good liquid crystal alignment properties, excellent pretilt angle expression ability, and excellent display reliability with little change in pretilt angle even after long-term operation. Furthermore, the liquid crystal display element produced by the method of the present invention has excellent display characteristics. DETAILED DESCRIPTION OF THE INVENTION

[0011] The liquid crystal aligning agent of the present invention is characterized by containing, as component (A), a polymer having a photoalignable group represented by the following formula (pa-1) and a solvent.

[0012] [ka]

[0013] In the formula, A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4- or 2,6-naphthylene, or phenylene, which is optionally substituted with a group selected from fluorine, chlorine, and cyano, or with an alkoxy group or a linear or branched alkyl residue having 1 to 5 carbon atoms (which is optionally substituted with one cyano group or one or more halogen atoms); R1 represents a single bond, an oxygen atom, -COO-, or -OCO-; R2 represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused ring group; R3 represents -COO- or -OCO-; R4 represents a monovalent organic group having 3 to 40 carbon atoms containing a linear or branched alkyl group or an alicyclic group having 1 to 40 carbon atoms; D represents an oxygen atom, a sulfur atom, or -NR d -(where R d represents a hydrogen atom or alkyl having 1 to 3 carbon atoms), a is an integer of 0 to 3, and * represents the bonding position.

[0014] The liquid crystal aligning agent may be such that the component (A) is a polymer further having a thermally crosslinkable group A and satisfies at least one of the following requirements Z1 and Z2. Z1: The polymer that is the component (A) further has a thermally crosslinkable group B. Z2: The component (B) further contains a compound having two or more thermally crosslinkable groups B in the molecule. The thermally crosslinkable group A and the thermally crosslinkable group B are each independently an organic group selected from the group consisting of a carboxyl group, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy moiety-containing group, an oxetanyl group, a thiiranyl group, an isocyanate group, and a blocked isocyanate group, and are selected so that the thermally crosslinkable group A and the thermally crosslinkable group B undergo a crosslinking reaction by heat, although the thermally crosslinkable group A and the thermally crosslinkable group B may be the same.

[0015] Here, "two or more in a molecule" means that the molecule contains two or more groups of the same type, such as two or more epoxy groups, as well as two or more different groups, such as a combination of an epoxy group and a thiirane group. Preferably, "two or more in a molecule" means that the molecule contains two or more groups of the same type.

[0016] The polymer, which is the component (A) contained in the liquid crystal aligning agent of the present invention, has high sensitivity to light, and therefore can exhibit alignment control ability even when irradiated with polarized ultraviolet light at a low exposure dose. Furthermore, when the polymer (A) contains not only a thermally crosslinkable group A but also a thermally crosslinkable group B, a crosslinking reaction involving the polymer (A) is possible even if the baking time of the liquid crystal alignment agent is short. This makes it easier for the anisotropy to remain (memory) in the liquid crystal alignment film when the photo-alignable moiety exhibits anisotropy due to a photoreaction, thereby improving the liquid crystal alignment and enabling the liquid crystal to exhibit a pretilt angle.

[0017] In addition, the photo-alignable group represented by the above formula (pa-1), the thermally crosslinkable group A, and the thermally crosslinkable group B can all be side chains in a polymer, and therefore can also be referred to as "side chains" as necessary. Each of the constituent elements of the present invention will be described in detail below.

[0018] <Component (A): Specific Polymer> [Photoalignment group represented by formula (pa-1)] In the present invention, the moiety having photoalignment property represented by the above formula (pa-1) in the molecule can be represented, for example, by the following formula (a-1). Furthermore, the moiety can be, but is not limited to, a structure derived from a monomer represented by the following formula (a-1-m). In the formula, Ia is a monovalent organic group represented by the following formula (pa-1).

[0019] [ka]

[0020] In formula (pa-1), A represents pyrimidine-2,5-diyl, pyridine-2,5-diyl, 2,5-thiophenylene, 2,5-furanylene, 1,4- or 2,6-naphthylene, or phenylene, which is optionally substituted with a group selected from fluorine, chlorine, and cyano, or with an alkoxy group or a linear or branched alkyl residue having 1 to 5 carbon atoms (which is optionally substituted with one cyano group or one or more halogen atoms); R1 represents a single bond, an oxygen atom, -COO-, or -OCO-; R2 represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused ring group; R3 represents -COO- or -OCO-; R4 represents a monovalent organic group having 3 to 40 carbon atoms containing a linear or branched alkyl group or an alicyclic group having 1 to 40 carbon atoms; D represents an oxygen atom, a sulfur atom, or -NR d -(where R d represents a hydrogen atom or alkyl having 1 to 3 carbon atoms), a is an integer of 0 to 3, and * represents the bonding position.

[0021] In the above formula (a-1) or (a-1-m), S a represents a spacer unit, and S a The linking group on the left of indicates that it is bonded to the main chain of a specific polymer, optionally via a spacer. S a can be represented by, for example, the structure of the following formula (Sp).

[0022] [ka]

[0023] In the formula (Sp), The left bond of W1 is M b represents a bond to The right bond of W3 is I a represents a bond to W1, W2, and W3 each independently represent a single bond, a divalent heterocycle, -(CH2) n - (wherein n represents 1 to 20), -OCH2-, -CHO-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CF2O-, -OCF2-, -CF2CF2- or -C≡C-, provided that one or more non-adjacent CH2 groups in these substituents can be independently substituted by -O-, -CO-, -CO-O-, -O-CO-, -Si(CH3)2-O-Si(CH3)2-, -NR-, -NR-CO-, -CO-NR-, -NR-CO-O-, -OCO-NR-, -NR-CO-NR-, -CH=CH-, -C≡C- or -O-CO-O- (wherein R independently represents hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms); A1 and A2 each independently represent a group selected from a single bond, a divalent alkyl group, a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group, and each group may be unsubstituted or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group.

[0024] In formula (a-1-m), M a represents a polymerizable group. Examples of the polymerizable group include radical polymerizable groups of (meth)acrylate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, (meth)acrylamide, and derivatives thereof, and siloxane. Preferred are (meth)acrylate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, and acrylamide. r is an integer satisfying the condition 1≦r≦3. M b is a group selected from a single bond, a (r+1)-valent heterocycle, a linear or branched alkyl group having 1 to 10 carbon atoms, a (r+1)-valent aromatic group, and a (r+1)-valent alicyclic group, and each group may be unsubstituted or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group, or a methoxy group.

[0025] A1, A 2、 and M b Examples of the aromatic group in A1 and A2 include aromatic hydrocarbons having 6 to 18 carbon atoms, such as benzene, biphenyl, and naphthalene. 2、 and M b Examples of the alicyclic group in A1 and A2 include alicyclic hydrocarbons having 6 to 12 carbon atoms, such as cyclohexane and bicyclohexane. 2、 and M b Examples of the heterocyclic ring in the formula include nitrogen-containing heterocyclic rings such as pyridine, piperidine, piperazine, etc. Examples of the alkyl group in A1 and A2 include linear or branched alkyl groups having 1 to 10 carbon atoms.

[0026] From the viewpoint of achieving good vertical alignment controllability and a stable pretilt angle, the group represented by (pa-1) above is preferably a group represented by (pa-1-a) below. Examples of this moiety include, but are not limited to, a structure derived from a monomer represented by the following formula (pa-1-ma):

[0027] [ka]

[0028] In formula (pa-1-a) or (pa-1-ma), M a , M b , and S a has the same definition as above. Furthermore, Z is an oxygen atom or a sulfur atom. 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. R1 is a single bond, an oxygen atom, -COO- or -OCO-. R2 is a divalent aromatic group, a divalent alicyclic group, or a divalent heterocyclic group. R3 is -COO- or -OCO-. R4 is a monovalent organic group having 3 to 40 carbon atoms and containing a linear or branched alkyl group or an alicyclic group having 1 to 40 carbon atoms. R5 is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a cyano group, preferably a methyl group, a methoxy group or a fluorine atom. a is an integer of 0 to 3, and b is an integer of 0 to 4.

[0029] In formula (pa-1-a) or (pa-1-ma), S a The linear or branched alkylene group having 1 to 10 carbon atoms is preferably a linear or branched alkylene group having 1 to 8 carbon atoms, and preferred examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a t-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, and an n-octylene group. S a Examples of the divalent aromatic group include a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, and a 2,3,5,6-tetrafluoro-1,4-phenylene group.

[0030] In formula (pa-1-a) or (pa-1-ma), S a Examples of the divalent alicyclic group include trans-1,4-cyclohexylene and trans-trans-1,4-bicyclohexylene. S a Examples of the divalent heterocyclic group include a 1,4-pyridylene group, a 2,5-pyridylene group, a 1,4-furanylene group, a 1,4-piperazine group, and a 1,4-piperidine group. S a is preferably an alkylene group having 1 to 8 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.

[0031] Examples of the divalent aromatic group for R2 include a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, a 2,3,5,6-tetrafluoro-1,4-phenylene group, and a naphthylene group. Examples of the divalent alicyclic group of R2 include trans-1,4-cyclohexylene and trans-trans-1,4-bicyclohexylene. Examples of the divalent heterocyclic group for R2 include a 1,4-pyridylene group, a 2,5-pyridylene group, a 1,4-furanylene group, a 1,4-piperazine group, and a 1,4-piperidine group. R2 may be a 1,4-phenylene group, trans 1,4-cyclohexylene, or trans-trans-1,4-bicyclohexylene.

[0032] Examples of the linear or branched alkyl group having 1 to 40 carbon atoms for R4 include linear or branched alkyl groups having 1 to 20 carbon atoms, in which some or all of the hydrogen atoms may be substituted with fluorine atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, n-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-lauryl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 4,4,4 -trifluorobutyl group, 4,4,5,5,5-pentafluoropentyl, 4,4,5,5,6,6,6-heptafluorohexyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2-(perfluorobutyl)ethyl group, 2-(perfluorooctyl)ethyl group, 2-(perfluorodecyl)ethyl group, and the like.

[0033] Examples of the monovalent organic group having 3 to 40 carbon atoms and containing an alicyclic group for R4 include a cholestenyl group, a cholestanyl group, an adamantyl group, and groups represented by the following formula (Alc-1) or (Alc-2) (wherein R7 is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 20 carbon atoms, which may be substituted with a fluorine atom, and * indicates the bonding position).

[0034] [ka]

[0035] Examples of the monomer represented by the formula (pa-1-ma) include the following formula (MA) (wherein S b represents a linear or branched alkyl group having 1 to 10 carbon atoms; R6 represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched alkyl group having 1 to 10 carbon atoms substituted with a halogen atom; R7 represents a single bond, an oxygen atom, -COO-, or -OCO-; R8 represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused ring group; R9 represents -COO- or -OCO-; 10 is a linear or branched alkyl group having 1 to 10 carbon atoms in which a hydrogen atom of the alkyl group may be substituted with a fluorine atom, and b represents an integer of 0 to 3.

[0036] [ka]

[0037] Examples of the monomer represented by the formula (pa-1-ma) include, but are not limited to, structures represented by formulas (paa-1-ma1) to (paa-1-ma38). In the formulas, "E" represents an E-form, and "t" represents a trans-form of the cyclohexyl group. In the formulas (paa-1-ma1) to (paa-1-ma38), n and m represent 1 to 10.

[0038] [ka]

[0039] [ka]

[0040] These monomers can be produced by combining known reactions, specifically by the methods described later in "Monomer Synthesis Examples."

[0041] [Thermal crosslinkable group A and thermal crosslinkable group B] 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, an amino group, an alkoxymethylamide group, a hydroxymethylamide group, a hydroxyl group, an epoxy moiety-containing group, an oxetanyl group, a thiiranyl group, an isocyanate group, and a blocked isocyanate group, and are selected so that the thermally crosslinkable group A and the thermally crosslinkable group B undergo a crosslinking reaction by heat, although the thermally crosslinkable group A and the thermally crosslinkable group B may be the same.

[0042] Combinations of such thermally crosslinkable groups A and B include a combination in which one is a carboxyl group and the other is an epoxy group, an oxetanyl group, or a thiiranyl group, a combination in which one is a hydroxyl group and the other is a blocked isocyanate group, a combination in which one is a phenolic hydroxyl group and the other is an epoxy group, an oxetanyl group, or a thiiranyl group, a combination in which one is a carboxyl group and the other is a blocked isocyanate group, a combination in which one is an amino group and the other is a blocked isocyanate group, a combination in which both are N-alkoxymethylamide, etc. More preferred combinations are a carboxyl group and an epoxy group, a hydroxyl group and a blocked isocyanate group, etc.

[0043] In order to introduce such a thermally crosslinkable group A into the polymer that is the component (A), it is sufficient to copolymerize a monomer having the thermally crosslinkable group A. In addition, when the liquid crystal aligning agent of the present invention satisfies the requirement Z1, it is sufficient to copolymerize both a monomer having the thermally crosslinkable group A and a monomer having the thermally crosslinkable group B when producing the polymer that is the component (A).

[0044] Examples of the monomer having a thermal 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;

[0045] Monomers having a hydroxy group, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2-(acryloyloxy)ethyl ester, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone;

[0046] Monomers having a phenolic hydroxy group, such as hydroxystyrene, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)maleimide, and N-(hydroxyphenyl)maleimide;

[0047] Monomers having an amino group, such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate;

[0048] (meth)acrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide;

[0049] Monomers having an epoxy moiety-containing group, such as allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, α-ethylglycidyl acrylate, α-n-propylglycidyl acrylate, α-n-butylglycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl-6,7-epoxyheptyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide;

[0050] 3-(acryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(acryloyloxymethyl)-2-phenyloxetane, 3-(acryloyloxymethyl)-2,2-difluorooxetane, 3-(acryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-acryloyloxy acrylic acid esters such as 3-(2-acryloyloxyethyl)oxetane, 3-(2-acryloyloxyethyl)-2-ethyloxetane, 3-(2-acryloyloxyethyl)-3-ethyloxetane, 3-(2-acryloyloxyethyl)-2-trifluoromethyloxetane, 3-(2-acryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-acryloyloxyethyl)-2-phenyloxetane, 3-(2-acryloyloxyethyl)-2,2-difluorooxetane, 3-(2-acryloyloxyethyl)-2,2,4-trifluorooxetane, and 3-(2-acryloyloxyethyl)-2,2,4,4-tetrafluorooxetane;3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-2-methyloxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-pentafluoroethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 3-(methacryloyloxymethyl)-2,2-difluorooxetane, 3-(methacryloyloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloyloxymethyl)-2,2,4,4-tetrafluorooxetane, 3-(2-methacryloyloxyethyl) monomers having an oxetanyl group, such as 3-(2-methacryloyloxyethyl)oxetane, 3-(2-methacryloyloxyethyl)-2-ethyloxetane, 3-(2-methacryloyloxyethyl)-3-ethyloxetane, 3-(2-methacryloyloxyethyl)-2-trifluoromethyloxetane, 3-(2-methacryloyloxyethyl)-2-pentafluoroethyloxetane, 3-(2-methacryloyloxyethyl)-2-phenyloxetane, 3-(2-methacryloyloxyethyl)-2,2-difluorooxetane, 3-(2-methacryloyloxyethyl)-2,2,4-trifluorooxetane, and 3-(2-methacryloyloxyethyl)-2,2,4,4-tetrafluorooxetane;

[0051] Monomers having a thiiranyl group, such as 2,3-epithiopropyl acrylate or methacrylate, and 2-, 3-, or 4-(β-epithiopropylthiomethyl)styrene, 2-, 3-, or 4-(β-epithiopropyloxymethyl)styrene, 2-, 3-, or 4-(β-epithiopropylthio)styrene, and 2-, 3-, or 4-(β-epithiopropyloxy)styrene;

[0052] Examples include monomers having a blocked isocyanate group, such as 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl acrylate, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl acrylate, 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate, and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate. Note that (meth)acrylamide refers to both acrylamide and methacrylamide.

[0053] Furthermore, in the present invention, when obtaining the specific copolymer, in addition to the monomer having a photoalignable group represented by the above formula (a-1-m) and the monomer having a thermal crosslinkable group A and, if necessary, a thermal crosslinkable group B, other monomers copolymerizable with these monomers can also be used in combination.

[0054] Specific examples of such other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, acrylamide compounds such as N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, and acrylamide, and monomers having a nitrogen-containing aromatic heterocyclic group and a polymerizable group.

[0055] Examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

[0056] Examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

[0057] Examples of the (meth)acrylic acid amide compound include acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, and N,N-diethylacrylamide.

[0058] Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, and 3-ethenyl-7-oxabicyclo[4.1.0]heptane.

[0059] Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

[0060] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0061] The nitrogen-containing aromatic heterocycle is preferably an aromatic cyclic hydrocarbon containing at least one, preferably 1 to 4, structures selected from the group consisting of the following formulae [Na] to [Nb] (wherein Z2 is a linear or branched alkyl group having 1 to 5 carbon atoms):

[0062] [ka]

[0063] Specific examples include an oxazole ring, a thiazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a 1-pyrazoline ring, an isoquinoline ring, a thiadiazole ring, a pyridazine ring, a triazine ring, a pyrazine ring, a phenanthroline ring, a quinoxaline ring, a benzothiazole ring, an oxadiazole ring, and an acridine ring. Furthermore, the carbon atom of these nitrogen-containing aromatic heterocycles may have a substituent containing a heteroatom. Among these, for example, a pyridine ring is mentioned.

[0064] Examples of monomers having a nitrogen-containing aromatic heterocyclic group and a polymerizable group include 2-(2-pyridylcarbonyloxy)ethyl (meth)acrylate, 2-(3-pyridylcarbonyloxy)ethyl (meth)acrylate, and 2-(4-pyridylcarbonyloxy)ethyl (meth)acrylate.

[0065] The other monomers used in the present invention may be used alone or in combination of two or more kinds.

[0066] The photoreactive moiety represented by the above formula (pa-1) to be contained in the polymer, which is the component (A) of the liquid crystal aligning agent of the present invention, may be one type alone or two or more types in combination.

[0067] The photoreactive moiety represented by the above formula (pa-1) is preferably contained in a proportion of 5 to 100 mol %, 10 to 60 mol %, or 15 to 50 mol % of all repeating units of the polymer that is component (A).

[0068] When the polymer of the present invention contains a thermally crosslinkable group, the moiety having the thermally crosslinkable group may be a thermally crosslinkable group A alone, or two or more moieties containing a thermally crosslinkable group A and a thermally crosslinkable group B may be used in combination.

[0069] When a moiety having a thermally crosslinkable group is introduced, the amount introduced is preferably 5 to 95 mol %, 10 to 70 mol %, or 15 to 50 mol % of all repeating units of the polymer that is component (A).

[0070] The content of the structure derived from the other monomers is preferably 0 to 60 mol %, 0 to 40 mol %, or 0 to 20 mol % of all repeating units of the polymer that is component (A).

[0071] <Method of producing specific polymer> The specific polymer of component (A) contained in the liquid crystal aligning agent of the present invention can be obtained by copolymerizing a monomer having a photoalignable group represented by the above formula (pa-1), optionally a monomer having the above thermal crosslinkable group A, and optionally a monomer having the above thermal crosslinkable group B. It can also be copolymerized with the other monomers described above.

[0072] The method for producing the specific polymer of component (A) in the present invention is not particularly limited, and a general-purpose method used industrially can be used. Specifically, the specific polymer can be produced by cationic polymerization, radical polymerization, or anionic polymerization using the vinyl group of the monomer. Among these, radical polymerization is particularly preferred from the viewpoint of ease of reaction control. As the polymerization initiator for radical polymerization, known compounds such as radical polymerization initiators and reversible addition-fragmentation chain transfer (RAFT) polymerization reagents can be used.

[0073] The radical thermal polymerization initiator is a compound that generates radicals when heated to a temperature equal to or higher than its decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), and azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.).

[0074] Such radical thermal polymerization initiators can be used alone or in combination of two or more.

[0075] The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include known compounds such as benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, and isopropylxanthone. These compounds may be used alone or in combination. The radical polymerization method is not particularly limited, and may be an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a bulk polymerization method, a solution polymerization method, or the like.

[0076] The solvent used in the polymerization reaction of the specific polymer of component (A) is not particularly limited as long as it dissolves the resulting polymer. Specific examples include the solvents described in the section below under "Solvent," such as N-alkyl-2-pyrrolidones, dialkylimidazolidinones, lactones, carbonates, ketones, compounds represented by formula (Sv-1) and formula (Sv-2), tetrahydrofuran, 1,4-dioxane, dimethyl sulfone, and dimethyl sulfoxide. These solvents may be used alone or in combination. Furthermore, even if a solvent does not dissolve the polymer to be produced, it may be mixed with the above-mentioned solvents to the extent that the polymer does not precipitate. In addition, since oxygen in the solvent inhibits the polymerization reaction in radical polymerization, it is preferable to use an organic solvent that has been degassed to the greatest extent possible.

[0077] The polymerization temperature during radical polymerization can be selected from any temperature between 30 and 150°C, but is preferably in the range of 50 to 100°C. The reaction can be carried out at any concentration, but the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction can be carried out at a high concentration in the early stages, and then an organic solvent can be added. In the above-mentioned radical polymerization reaction, if the ratio of the radical polymerization initiator to the monomer is high, the molecular weight of the resulting polymer will be small, and if it is low, the molecular weight of the resulting polymer will be large, so the ratio of the radical initiator to the monomer to be polymerized is preferably 0.1 to 10 mol %. Furthermore, various monomer components, solvents, initiators, etc. can also be added during polymerization.

[0078] [Polymer recovery] To recover the polymer produced from the reaction solution obtained by the above-mentioned reaction, the reaction solution may be poured into a poor solvent to precipitate the polymer. Examples of poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer precipitated by pouring into the poor solvent can be recovered by filtration and then dried at room temperature or by heating under atmospheric or reduced pressure. Furthermore, the precipitated polymer can be redissolved in an organic solvent and reprecipitated and recovered two to ten times to reduce the amount of impurities in the polymer. Examples of poor solvents include alcohols, ketones, and hydrocarbons. Using three or more poor solvents selected from these solvents is preferred because it further increases the efficiency of purification.

[0079] The molecular weight of the specific polymer of component (A) is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000, in terms of weight average molecular weight measured by GPC (Gel Permeation Chromatography), taking into consideration the strength of the resulting coating film, workability during coating film formation, and uniformity of the coating film.

[0080] <(B) component> When the liquid crystal aligning agent used in the present invention satisfies the requirement Z2, it contains a crosslinking agent as the component (B). The component (B) may be a crosslinking agent having two or more thermally crosslinkable groups B.

[0081] Examples of the crosslinking agent as component (B) include low molecular weight compounds such as epoxy compounds, compounds having two or more amino groups, methylol compounds, isocyanate compounds, phenoplast compounds, and blocked isocyanate compounds, as well as polymers such as polymers of N-alkoxymethylacrylamide, polymers of compounds having epoxy groups, and polymers of compounds having isocyanate groups.

[0082] Specific examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane.

[0083] Examples of compounds having two or more amino groups include diamines such as alicyclic diamines, aromatic diamines, aromatic-aliphatic diamines, and aliphatic diamines.

[0084] Examples of the alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexylamine, and isophoronediamine.

[0085] 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.

[0086] Examples of aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3-(3-aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methylaminopropyl)aniline, 3-(4- ... 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, 2-(6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, 3-(6-aminonaphthyl)ethylamine, and the like.

[0087] Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, and 1,9-diamino-5-methylheptane.

[0088] Specific examples of the methylol compound include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

[0089] Specific examples of alkoxymethylated glycolurils include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins (high condensation type, trade names: Beckamin (registered trademark) J-300S, P-955, N) manufactured by DIC Corporation.

[0090] Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123) and those manufactured by Sanwa Chemical Co., Ltd. (trade names: Nikalac (registered trademark) BX-4000, BX-37, BL-60, and BX-55H).

[0091] Specific examples of alkoxymethylated melamine include hexamethoxymethyl melamine, etc. Commercially available products include methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, and 350) and butoxymethyl type melamine compounds (trade names: Mycoat (registered trademark) 506 and 508) manufactured by Mitsui Cytec Co., Ltd., and methoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, and MX-035) and butoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MX-45, MX-410, and MX-302) manufactured by Sanwa Chemical Co., Ltd.

[0092] The compound may also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, or a benzoguanamine compound in which the hydrogen atom of the amino group has been substituted with a methylol group or an alkoxymethyl group. Examples include high-molecular-weight compounds produced from melamine compounds and benzoguanamine compounds described in U.S. Patent No. 6,323,310. Commercially available melamine compounds include Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available benzoguanamine compounds include Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

[0093] Specific examples of the isocyanate compound include VESTANAT B1358 / 100 and VESTAGON BF 1540 (both are isocyanurate-modified polyisocyanates, manufactured by Degussa Japan Co., Ltd.), Takenate (registered trademark) B-882N and Takenate B-7075 (both are isocyanurate-modified polyisocyanates, manufactured by Mitsui Chemicals, Inc.), and the like.

[0094] Specific examples of the phenoplast compound include the following compounds, but the phenoplast compound is not limited to the following compound examples.

[0095] [ka]

[0096] Specific examples of the compound having two or more hydroxyalkylamide groups at the molecular terminal include the following compounds, Primid XL-552, and Primid SF-4510.

[0097] [ka]

[0098] Examples of blocked isocyanate compounds include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, and Millionate MS-50 (all manufactured by Nippon Polyurethane Industry Co., Ltd.), and Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, and B-882N (all manufactured by Mitsui Chemicals, Inc.).

[0099] Furthermore, examples of the above-mentioned N-alkoxymethylacrylamide polymers include polymers produced using acrylamide compounds or methacrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide.

[0100] Specific examples of such polymers include poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate, etc. The weight-average molecular weight of such polymers is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

[0101] Examples of polymers of compounds having an epoxy group include polymers produced using compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate.

[0102] Specific examples of such polymers include poly(3,4-epoxycyclohexylmethyl methacrylate), poly(glycidyl methacrylate), a copolymer of glycidyl methacrylate and methyl methacrylate, a copolymer of 3,4-epoxycyclohexylmethyl methacrylate and methyl methacrylate, a copolymer of glycidyl methacrylate and styrene, etc. The weight-average molecular weight of such polymers is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

[0103] Examples of the polymer of the compound having an isocyanate group described above include polymers produced using a compound having an isocyanate group, such as 2-isocyanatoethyl methacrylate (Karenz MOI [registered trademark], manufactured by Showa Denko K.K.) or 2-isocyanatoethyl acrylate (Karenz AOI [registered trademark], manufactured by Showa Denko K.K.), or a compound having a blocked isocyanate group, such as 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (Karenz MOI-BM [registered trademark], manufactured by Showa Denko K.K.) or 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP [registered trademark], manufactured by Showa Denko K.K.).

[0104] Specific examples of such polymers include poly(2-isocyanatoethyl acrylate), poly(2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate), a copolymer of 2-isocyanatoethyl methacrylate and styrene, and a copolymer of 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate and methyl methacrylate. The weight-average molecular weight of such polymers is 1,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000.

[0105] These crosslinking agents can be used alone or in combination of two or more.

[0106] When the liquid crystal aligning agent used in the present invention contains the crosslinking agent of the component (B), the content thereof is preferably 1 to 100 parts by mass, more preferably 1 to 80 parts by mass, based on 100 parts by mass of the resin of the component (A).

[0107] [Preparation of liquid crystal alignment agent] The liquid crystal aligning agent used in the present invention is preferably prepared as a coating liquid suitable for forming a liquid crystal alignment film. That is, the liquid crystal aligning agent of the present invention is preferably prepared as a solution in which a resin component for forming a resin coating is dissolved in an organic solvent. Here, the resin components are the specific polymer (component (A)) and the polymer (component (B)) already explained. In this case, the total content of the specific polymer (component (A)) and the polymer (component (B)) is preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, even more preferably 1 to 15% by mass, and particularly preferably 1 to 10% by mass, based on the total amount of the liquid crystal aligning agent.

[0108] <(C) component> The liquid crystal aligning agent of the present invention can contain, as component (C), a polymer selected from polyimides and their precursors, which has at least one group selected from a vertically aligning group and a tertiary-butoxycarbonyl group, or is chemically imidized.

[0109] The liquid crystal aligning agent of the present invention contains a polymer as component (C), which can further improve electrical properties such as an improved voltage holding ratio and suppression of residual charge accumulation.

[0110] The polymer of component (C) is a polyimide or its precursor (hereinafter also referred to as the polyimide component), and has a surface energy similar to that of the polymer of component (A). Acrylic components such as component (A) generally have low polarity and low surface energy. On the other hand, polyimide components have high polarity and high surface energy. However, if the difference in surface energy between these two components is too large, they may not be compatible and may aggregate, resulting in uneven films or narrow process margins due to cissing and unevenness. Therefore, by reducing the polarity of the polyimide component, the surface energy can be controlled to a value higher than that of the acrylic component, but with a small difference. Methods for reducing the polarity of the polyimide component include chemical imidization followed by mixing with component (A) or introducing side chains.

[0111] Examples of such polymers include polymers obtained by polymerizing a tetracarboxylic acid derivative such as a known tetracarboxylic acid dianhydride with a known diamine and then chemically imidizing the polymer; polyimide precursors obtained using diamines with side chains and then imidizing the precursors; and polyimides obtained by imidizing the precursors using diamines with tertiary butoxycarbonyloxy groups. These side chains and chemical imidization can bring the surface energy closer to that of the acrylic polymer (component (A)). Therefore, when a liquid crystal alignment agent is applied and baked to form a cured film, aggregation does not occur, resulting in a flat cured film. Examples of diamines with side chains include diamines represented by formulas (2), (3), (4), and (5), as described in paragraphs

[0023] to

[0039] of International Patent Application Publication WO 2016 / 125870, and specific examples thereof are diamines represented by formulas [A-1] to [A-32]. Examples of diamines having a tertiary-butoxycarbonyloxy group include diamines having structures of formulas [A-1], [A-2], and [A-3] described in paragraphs

[0011] to

[0034] of International Patent Application Publication WO2017 / 119461, and diamines exemplified as specific examples thereof.

[0112] When the liquid crystal aligning agent of the present invention contains a polymer as component (C), the content ratio of component (A):component (C) is preferably 5:95 to 95:5 by mass, more preferably 10:90 to 90:10, and even more preferably 20:80 to 60:40.

[0113] <Solvent> The solvent contained in the liquid crystal aligning agent used in the present invention is not particularly limited as long as it is a solvent that can dissolve component (A), optionally component (B), and optionally component (C). The solvent contained in the liquid crystal aligning agent may be one type, or two or more types may be mixed and used. Furthermore, even if the solvent does not dissolve component (A) or (B), it can be used in combination with a solvent that dissolves component (A) or (B). In this case, it is preferable that the surface energy of the solvent that does not dissolve component (A) or (B) is lower than that of the solvent that dissolves component (A) or (B), because this improves the coatability of the liquid crystal aligning agent to the substrate.

[0114] Specific examples include water, N-alkyl-2-pyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylcaprolactam, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, dialkylimidazolidinones such as 1,3-dimethyl-2-imidazolidinone, lactones such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone, carbonates such as ethylene carbonate and propylene carbonate, methanol, ethanol, propanol, isopropanol, 3-methyl-3-methylpropanamide, methylpropanol ... Examples of suitable ketones include hydroxybutanol, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, isoamyl methyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, and 4-hydroxy-4-methyl-2-pentanone; compounds represented by the following formula (Sv-1) and the following formula (Sv-2); 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, isoamyl butyrate, diisobutyl carbinol, and diisopentyl ether.

[0115] [ka]

[0116] In formulas (Sv-1) to (Sv-2), Y1 and Y2 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, X1 is an oxygen atom or -COO-, X2 is a single bond or a carbonyl group, and R1 is an alkanediyl group having 2 to 4 carbon atoms. n1 is an integer of 1 to 3. When n1 is 2 or 3, multiple R1s may be the same or different. Z1 is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Y3 and Y4 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

[0117] In formula (Sv-1), examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms for Y1 and Y2 include a monovalent chain hydrocarbon group having 1 to 6 carbon atoms, a monovalent alicyclic hydrocarbon group having 1 to 6 carbon atoms, and a monovalent aromatic hydrocarbon group having 1 to 6 carbon atoms. Examples of the monovalent chain hydrocarbon group having 1 to 6 carbon atoms include an alkyl group having 1 to 6 carbon atoms. The alkanediyl group for R1 may be linear or branched.

[0118] In formula (Sv-2), examples of the divalent hydrocarbon group having 1 to 6 carbon atoms for Z1 include an alkanediyl group having 1 to 6 carbon atoms. Examples of the monovalent hydrocarbon groups having 1 to 6 carbon atoms for Y3 and Y4 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. Examples of the monovalent chain hydrocarbon groups having 1 to 6 carbon atoms include alkyl groups having 1 to 6 carbon atoms.

[0119] Specific examples of the solvent represented by formula (Sv-1) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, propylene glycol diacetate, ethylene glycol, 1,4-butanediol, 3-methoxybutyl acetate, and 3-ethoxybutyl acetate; Specific examples of the solvent represented by (Sv-2) include methyl glycolate, ethyl glycolate, butyl glycolate, ethyl lactate, butyl lactate, isoamyl lactate, ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, and butyl 3-methoxypropionate.

[0120] The solvent preferably has a boiling point of 80 to 200° C. More preferably, it is 80 to 180° C. Preferred solvents include N,N-dimethylformamide, tetramethylurea, 3-methoxy-N,N-dimethylpropanamide, propanol, isopropanol, 3-methyl-3-methoxybutanol, ethyl amyl ketone, methyl ethyl ketone, isoamyl methyl ketone, methyl isopropyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, 4-hydroxy-4-methyl-2-pentanone, 4-methyl-2-pentyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, butyl butyrate, and butyl methyl ketone. Examples of the lactate include isoamyl lactate, diisobutyl carbinol, diisopentyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol 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, and ethyl 3-methoxypropionate. The boiling point being in this range is particularly preferable when the liquid crystal aligning agent containing the solvent is applied onto a plastic substrate, which will be described later.

[0121] <Other ingredients> The liquid crystal aligning agent used in the present invention may contain other components in addition to the above-mentioned component (A), if necessary the component (B), and if necessary the component (C). Examples of such other components include, but are not limited to, a crosslinking catalyst, a compound that improves the film thickness uniformity and surface smoothness when the liquid crystal aligning agent is applied, and a compound that improves the adhesion between the liquid crystal alignment film and the substrate.

[0122] <Crosslinking catalyst> A crosslinking catalyst may be added to the liquid crystal aligning agent used in the present invention for the purpose of promoting the reaction between the thermally crosslinkable group A and the thermally crosslinkable group B. Examples of such a crosslinking catalyst include sulfonic acids such as p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, and dodecylbenzenesulfonic acid, or hydrates or salts thereof. Examples of compounds that generate an acid when heated include bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylene tris(methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, and N-ethyl-p-toluenesulfonamide.

[0123] [Compounds that improve film thickness uniformity and surface smoothness] Compounds that improve the uniformity of the film thickness and the surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples include F-TOP (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), MEGAFAC (registered trademark) F171, F173, R-30 (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and the like. The proportion of these surfactants used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the polymer composition.

[0124] [Compounds that improve adhesion between liquid crystal alignment film and substrate] Specific examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine , 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, and N-bis(oxyethylene)-3-aminopropyltriethoxysilane, and other amino-based silane-containing compounds.

[0125] When a compound that improves adhesion to the substrate is used, the amount used is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, per 100 parts by mass of the resin component contained in the polymer composition.

[0126] In some embodiments, a photosensitizer can be used as an additive to improve the photoreactivity of the photoalignment group. Specific examples include aromatic 2-hydroxyketones (benzophenones), coumarins, ketocoumarins, carbonylbiscoumarins, acetophenones, anthraquinones, xanthones, thioxanthones, and acetophenone ketals.

[0127] <Liquid crystal alignment film and liquid crystal display element> The liquid crystal aligning agent of the present invention can be applied to a substrate, baked, and then subjected to alignment treatment such as rubbing or light irradiation to form a liquid crystal alignment film, or, for some vertical alignment applications, can be used without alignment treatment. Examples of substrates that can be used include glass such as float glass and soda glass, and transparent substrates made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polypropylene, polystyrene, polyethersulfone, polycarbonate, poly(alicyclic olefin), polyvinyl chloride, polyvinylidene chloride, polyetheretherketone (PEEK) resin film, polysulfone (PSF), polyethersulfone (PES), polyamide, polyimide, acrylic, and triacetyl cellulose. The transparent conductive film provided on one side of the substrate may be a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO2), an ITO film made of indium oxide-tin oxide (In2O3-SnO2), or the like.

[0128] <Coating film formation process> The method for applying the liquid crystal aligning agent of the present invention is not particularly limited, and examples thereof include screen printing, flexographic printing, offset printing, inkjet printing, dip coating, roll coating, slit coating, spin coating, etc., which may be used depending on the purpose. After applying the agent to a substrate by these methods, the solvent is evaporated by a heating means such as a hot plate to form a coating film.

[0129] The baking after application of the liquid crystal alignment agent can be carried out at any temperature between 40 and 300°C, preferably between 40 and 250°C, and more preferably between 40 and 230°C. The thickness of the coating film formed on the substrate is preferably 5 to 1,000 nm, more preferably 10 to 500 nm or 10 to 300 nm. This baking can be carried out using a hot plate, a hot air circulating oven, an infrared oven, or the like. For the rubbing treatment, a rayon cloth, a nylon cloth, a cotton cloth, or the like can be used.

[0130] <Light irradiation process> In one embodiment, an alignment treatment by light irradiation may be performed, and may include, for example, a step of applying the above-mentioned liquid crystal alignment agent onto a substrate to form a coating film, and a step of irradiating the coating film with light while the coating film is not in contact with the liquid crystal layer or while the coating film is in contact with the liquid crystal layer.

[0131] Examples of light to be irradiated in the alignment treatment by light irradiation include ultraviolet light and visible light having a wavelength of 150 to 800 nm. Of these, ultraviolet light having a wavelength of 300 to 400 nm is preferred. The irradiated light may be polarized or unpolarized. As the polarized light, it is preferred to use light including linearly polarized light.

[0132] When the light used is polarized light, the light may be irradiated from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these. When irradiating with unpolarized light, the light is preferably irradiated from an oblique direction relative to the substrate surface. The light irradiation dose was 0.1 mJ / cm 2 More than 1,000mJ / cm 2 It is preferable that the dose is less than 1 to 500 mJ / cm 2 It is more preferable to set the dose to 2 to 200 mJ / cm. 2 It is more preferable to set the following.

[0133] The liquid crystal display element of the present invention can be produced by a conventional method, and the production method is not particularly limited. The pair of substrates are opposed to each other with an appropriate gap therebetween, and it is preferable to place spacers between the substrates in order to make the thickness of the liquid crystal sandwiched between the substrates uniform. As the spacers, known spacer materials such as conventional dispersed spacers and spacers formed from a photosensitive spacer-forming composition can be used, and it is also possible to use irregularities formed in a layer made of a cured liquid crystal product as spacers.

[0134] <Liquid crystal clamping process> There are two methods for constructing a liquid crystal cell by sandwiching liquid crystal between substrates: The first method involves arranging a pair of substrates facing each other with a gap (cell gap) between them so that the liquid crystal alignment films face each other, bonding the peripheries of the pair of substrates together using a sealant, injecting liquid crystal onto the substrate surfaces and into the cell gap defined by an appropriate sealant, and then sealing the injection hole to produce a liquid crystal cell.

[0135] A second method is a method (ODF (One Drop Fill) method) in which, for example, an ultraviolet light-curable sealant is applied to a predetermined location on one of two substrates on which a liquid crystal alignment film has been formed, and liquid crystal is then dropped onto several predetermined locations on the liquid crystal alignment film surface.The other substrate is then attached so that the liquid crystal alignment film faces the other substrate, and the liquid crystal is spread over the entire surface of the substrate.Then, ultraviolet light is irradiated onto the entire surface of the substrate to cure the sealant, thereby manufacturing a liquid crystal cell.

[0136] As the liquid crystal, a fluorine-based liquid crystal or a cyano-based liquid crystal having positive or negative dielectric anisotropy may be used depending on the application, or a liquid crystal compound or liquid crystal composition that is polymerized by at least one of heating and light irradiation (hereinafter also referred to as a polymerizable liquid crystal or a curable liquid crystal composition). In one embodiment, the step of forming a coating film of the liquid crystal alignment agent may be performed by a roll-to-roll process, which simplifies the manufacturing process of the liquid crystal display element and reduces manufacturing costs. Then, a polarizing plate is attached to both outer surfaces of the liquid crystal cell, thereby obtaining a liquid crystal display element.

[0137] Examples of polarizing plates used on the outside of a liquid crystal cell include polarizing plates in which a polarizing film called an "H film" made by stretching and aligning polyvinyl alcohol and absorbing iodine is sandwiched between cellulose acetate protective films, or polarizing plates made of the H film itself. The liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention as described above has good liquid crystal alignment properties, is excellent in pretilt angle expression ability, and is highly reliable. Furthermore, the liquid crystal display element produced by the method of the present invention has excellent display characteristics. [Example]

[0138] The abbreviations used in the examples are as follows: <Methacrylic monomer> (Photo-alignable monomer)

[0139] [ka]

[0140] MA-1 to MA-7 are novel compounds not yet published in the literature, and their synthesis methods are described in detail in the following Monomer Synthesis Examples 1 to 7. MA-8 was synthesized by the synthesis method described in patent document (WO-2017115790). MA-9 was synthesized by the synthesis method described in patent document (WO-2017115790).

[0141] The abbreviations for the organic solvents used in the examples are as follows: NMP: N-methyl-2-pyrrolidone. BCS: butyl cellosolve. THF: tetrahydrofuran. DMAc: N,N-dimethylacetamide. PhMe: toluene. CHCl2: methylene chloride. MeCN: acetonitrile.

[0142] < 1 HNMR Measurement Equipment: Fourier transform superconducting nuclear magnetic resonance spectrometer (FT-NMR) "AVANCE III" (BRUKER) 500MHz. Solvent: deuterated chloroform (CDCl3) or deuterated N,N-dimethyl sulfoxide ([D6]-DMSO). Standard substance: tetramethylsilane (TMS).

[0143] (polar monomer) MAA: methacrylic acid

[0144] [ka]

[0145] (Crosslinking monomer) GMA: Glycidyl methacrylate

[0146] [ka]

[0147] (Isocyanate Monomer) MOI-BP: 2-[(3,5-dimethyl-1-pyrazolyl)carbonylamino]ethyl methacrylate

[0148] [ka]

[0149] <Tetracarboxylic acid dianhydride monomer> A1: Tetracarboxylic acid dianhydride represented by the following formula [A1] A2: Tetracarboxylic acid dianhydride represented by the following formula [A2] A3: Tetracarboxylic acid dianhydride represented by the following formula [A3] A4: Tetracarboxylic acid dianhydride represented by the following formula [A4] A5: Tetracarboxylic acid dianhydride represented by the following formula [A5] A6: Tetracarboxylic acid dianhydride represented by the following formula [A6] A7: Tetracarboxylic acid dianhydride represented by the following formula [A7] A8: Tetracarboxylic acid dianhydride represented by the following formula [A8]

[0150] [ka]

[0151] <Side chain diamine monomer> B1: a side chain diamine monomer represented by the following formula [B1] B2: a side chain diamine monomer represented by the following formula [B2] B3: a side chain diamine monomer represented by the following formula [B3] B4: a side chain diamine monomer represented by the following formula [B4] B5: a side chain diamine monomer represented by the following formula [B5] B6: a side chain diamine monomer represented by the following formula [B6] B7: a side chain diamine monomer represented by the following formula [B7] B8: A side chain diamine monomer represented by the following formula [B8] B9: a side chain diamine monomer represented by the following formula [B9] B10: A side chain diamine monomer represented by the following formula [B10] B11: A side chain diamine monomer represented by the following formula [B11] B12: a side chain diamine monomer represented by the following formula [B12] B13: A side chain diamine monomer represented by the following formula [B13] B14: A side chain diamine monomer represented by the following formula [B14]

[0152] [ka]

[0153] [ka]

[0154] <Other diamine monomers> C1: Other diamine monomers represented by the following formula [C1] C2: Other diamine monomers represented by the following formula [C2] C3: Other diamine monomers represented by the following formula [C3] C4: Other diamine monomers represented by the following formula [C4] C5: Other diamine monomers represented by the following formula [C5] C6: Other diamine monomers represented by the following formula [C6] C7: Other diamine monomers represented by the following formula [C7] C8: Other diamine monomers represented by the following formula [C8] C9: Other diamine monomers represented by the following formula [C9] C10: Other diamine monomers represented by the following formula [C10] C11: Other diamine monomers represented by the following formula [C11] C12: Other diamine monomers represented by the following formula [C12] C13: Other diamine monomers represented by the following formula [C13] C14: Other diamine monomers represented by the following formula [C14] C15: Other diamine monomers represented by the following formula [C15] C16: Other diamine monomers represented by the following formula [C16] C17: Other diamine monomers represented by the following formula [C17] C18: Other diamine monomers represented by the following formula [C18] C19: Other diamine monomers represented by the following formula [C19] C20: Other diamine monomers represented by the following formula [C20]

[0155] [ka]

[0156] [ka]

[0157] (Crosslinking agent component) D1: a crosslinker component represented by the following formula [D1] D2: a crosslinker component represented by the following formula [D2] D3: a crosslinker component represented by the following formula [D3]

[0158] [ka]

[0159] The abbreviations for the other reagents used in this example are shown below. (Polymerization initiator) AIBN: Azobisisobutyronitrile (solvent) NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve THF: tetrahydrofuran DMF: N,N-dimethylformamide

[0160] (molecular weight measurement) The molecular weights of the polymers in the synthesis examples were measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co., Ltd. Column temperature: 50°C, eluent: DMF (additives: lithium bromide hydrate (LiBr·H2O) 30 mmol / L, phosphoric acid anhydrous crystal (o-phosphoric acid) 30 mmol / L, THF 10 ml / L), flow rate: 1.0 ml / min Standard samples for preparing calibration curves: TSK standard polyethylene oxide (molecular weights approximately 9,000,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weights approximately 12,000, 4,000, and 1,000) manufactured by Polymer Laboratory.

[0161] (Imidization rate measurement) The imidization rate in the synthesis examples was measured as follows. 20 mg of polyimide powder was placed in an NMR sample tube (Kusano Scientific NMR Sampling Tube Standard, φ5), 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS mixture) was added, and the solution was sonicated to completely dissolve it. This solution was measured by 500 MHz proton NMR using a JEOL Datum NMR spectrometer (JNW-ECA500). The proton derived from the structure that remained unchanged before and after imidization was determined as the reference proton. The imidization rate was calculated using the integrated peak value of this proton and the integrated peak value of the proton derived from the NH group of the amic acid, which appeared around 9.5 to 10.0 ppm, according to the following formula: In the formula, x is the integrated peak value of the proton derived from the NH group of the amic acid, y is the integrated peak value of the reference proton, and α is the ratio of the number of reference protons to one proton of the NH group of the amic acid in the case of polyamic acid (with an imidization rate of 0%). Imidization rate (%) = (1 - α x / y) x 100

[0162] (Monomer synthesis example 1) Synthesis of [MA-1]:

[0163] [ka]

[0164] A 2L four-neck flask was charged with trans-4-(4-bromophenyl)cyclohexanol (190.0 g, 740 mmol), tert-butyl acrylate (114.2 g, 890 mmol), tripropylamine (264.9 g, 1850 mmol), and PhMe (950 g). After purging with nitrogen, palladium(II) acetate (3.3 g, 15 mmol) and tri(o-tolyl)phosphine (9.0 g, 30 mmol) were added and stirred at 100 °C. After completion of the reaction, the reaction solution was poured into 0.5N aqueous hydrochloric acid (500 g). After extraction, the organic layer was washed with purified water (1000 g) and concentrated. Hexane (1000 g) was added to the resulting crude product, and the mixture was repulped and washed at 0 °C to obtain 169.8 g of [MA-1-1].

[0165] A 1 L four-neck flask was charged with [MA-1-1] (50.0 g, 137 mmol), 4,4,4-trifluorobutyric acid (26.4 g, 186 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (48.9 g, 254 mmol), 4-dimethylaminopyridine (2.1 g, 17 mmol), and THF (500 g) and stirred at room temperature. After completion of the reaction, the reaction solution was poured into purified water (2500 g), and the precipitate was filtered off. Ethyl acetate (1500 g) was added to the resulting crude product to completely dissolve it, and the organic layer was washed with purified water (1500 g) and concentrated. Hexane (300 g) was added to the resulting crude product, and the mixture was repulped and washed at room temperature to yield 58.5 g of [MA-1-2].

[0166] [MA-1-2] (58.5 g, 137 mmol) and formic acid (590 g) were charged into a 1 L four-neck flask and stirred at 50 °C. After the reaction was completed, the reaction solution was poured into pure water (3000 g) and the precipitate was filtered off. Acetonitrile (500 g) was added to the obtained crude product, and the mixture was repulped and washed at room temperature to obtain 46.9 g of [MA-1-3].

[0167] A 1L four-neck flask was charged with [MA-1-3] (46.9 g, 127 mmol), 2-hydroxyethyl methacrylate (18.1 g, 139 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (36.4 g, 190 mmol), 4-dimethylaminopyridine (1.5 g, 13 mmol), and THF (470 g), and the mixture was stirred at room temperature. After the reaction was completed, the reaction solution was concentrated, and ethyl acetate (500 g) was poured into the resulting residue. The organic layer was washed with pure water (1500 g) and concentrated. The resulting crude product was subjected to origin cut with silica gel using an ethyl acetate / hexane (volume ratio 1:3). Hexane (400 g) was then added to the resulting crude product, and the mixture was repulped and washed at room temperature, yielding 55.2 g of [MA-1] (white solid). 1 The results of H-NMR are shown below, and it was confirmed that the obtained solid was the desired [MA-1]. 1 H NMR (500 MHz, [D6]-DMSO):δ7.62-7.65 (m,3H), 7.30-7.31 (d,2H), 6.59-6.62 (d,1H), 6.04 (s,1H), 5.70 (s,1H), 4.73-4.78 (m,1H), 4.40-4.42 (m,2H), 4.36-4.37 (m,2H), 2.52-2.60 (m,5H), 1.99-2.02 (d,2H), 1.88 (s,3H), 1.81-1.84 (d,2H), 1.56-1.62 (m,2H), 1.47-1.53 (m,2H)

[0168] (Monomer synthesis example 2) Synthesis of [MA-2]:

[0169] [ka]

[0170] A 2L four-neck flask was charged with 4-bromo-4'-hydroxybiphenyl (99.6g, 400mmol), tert-butyl acrylate (102.5g, 800mmol), tripropylamine (143.3g, 1000mmol), and DMAc (500g). After purging with nitrogen, palladium(II) acetate (3.6g, 16mmol) and tri(o-tolyl)phosphine (9.7g, 32mmol) were added and stirred at 100°C. After completion of the reaction, the reaction solution was poured into 0.5N aqueous hydrochloric acid (1000g), extracted with ethyl acetate (2500g), and the organic layer was washed with purified water (2000g) and concentrated. The obtained crude material was subjected to origin cut with silica gel using an ethyl acetate / hexane (volume ratio 1:3) solution, and further, hexane (500 g) was added to the obtained crude material and repulp washed at room temperature to obtain 112.9 g of [MA-2-1].

[0171] A 1 L four-neck flask was charged with [MA-2-1] (32.8 g, 110 mmol), 4,4,4-trifluorobutyric acid (17.3 g, 122 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (31.9 g, 166 mmol), 4-dimethylaminopyridine (1.4 g, 11 mmol), and THF (330 g) and stirred at room temperature. After completion of the reaction, the reaction solution was poured into purified water (2000 g), and the precipitate was filtered off. Ethyl acetate (600 g) was added to the resulting crude product to completely dissolve it, and the organic layer was washed with purified water (1500 g) and concentrated. Hexane (200 g) was added to the resulting crude product, and the mixture was repulped and washed at room temperature to yield 43.8 g of [MA-2-2].

[0172] A 2 L four-neck flask was charged with [MA-2-2] (43.8 g, 104 mmol) and formic acid (440 g) and stirred at 50 °C. After the reaction was completed, the reaction solution was poured into pure water (2500 g) and the precipitate was filtered off. Acetonitrile (400 g) was added to the obtained crude product, and the mixture was repulped and washed at room temperature to obtain 35.9 g of [MA-2-3].

[0173] A 1 L four-neck flask was charged with [MA-2-3] (35.9 g, 99 mmol), 2-hydroxyethyl methacrylate (14.1 g, 109 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (28.4 g, 148 mmol), 4-dimethylaminopyridine (1.2 g, 10 mmol), and THF (360 g), and the mixture was stirred at room temperature. After the reaction was completed, the reaction solution was poured into pure water (2000 g), and the precipitate was filtered off. Ethyl acetate (1500 g) was added to the obtained crude product to completely dissolve it, and the organic layer was washed with pure water (3000 g) and concentrated. The obtained crude product was subjected to origin cut with silica gel using an ethyl acetate / hexane (volume ratio 1:2). Hexane (200 g) was added to the obtained crude product, and the product was repulped and washed at room temperature, yielding 40.9 g of [MA-2] (white solid). 1 The results of H-NMR are shown below, and it was confirmed that the obtained solid was the desired [MA-2]. 1 H NMR (500 MHz, [D6]-DMSO):δ7.83-7.84 (d,2H), 7.78-7.80 (d,2H), 7.71-7.75 (m,3H), 7.24-7.26 (d,2H), 6.71-6.74 (d,1H), 6.06 (s,1H), 5.71 (s,1H), 4.43-4.45 (m,2H), 4.38-4.39 (m,2H), 2.90-2.93 (t,2H), 2.67-2.73 (m,2H), 1.89 (s,3H)

[0174] (Monomer Synthesis Example 3) Synthesis of [MA-3]:

[0175] [ka]

[0176] A 1 L four-neck flask was charged with tert-butyl 4-hydroxybenzoate (24.3 g, 125 mmol), 4,4,4-trifluorobutyric acid (19.5 g, 138 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (36.0 g, 188 mmol), 4-dimethylaminopyridine (1.5 g, 13 mmol), and THF (240 g) and stirred at room temperature. After completion of the reaction, the reaction mixture was poured into ethyl acetate (300 g), and the organic layer was washed with purified water (900 g) and concentrated. Hexane (400 g) was added to the resulting crude product, which was then repulped and washed at 0 °C to yield 35.9 g of [MA-3-1].

[0177] [MA-3-1] (35.9 g, 113 mmol) and formic acid (360 g) were placed in a 1 L four-neck flask and stirred at 50° C. After the reaction was completed, the reaction solution was poured into pure water (2000 g), and the precipitate was filtered and dried to obtain 27.8 g of [MA-3-2].

[0178] A 1 L four-neck flask was charged with [MA-3-2] (27.8 g, 106 mmol), trans-p-tert-butyl coumarate (32.6 g, 148 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (30.4 g, 159 mmol), 4-dimethylaminopyridine (1.3 g, 11 mmol), and THF (280 g) and stirred at room temperature. After completion of the reaction, the reaction solution was poured into purified water (2500 g), and the precipitate was filtered off. Ethyl acetate (2500 g) was added to the obtained crude product to completely dissolve it, and the organic layer was washed with purified water (3000 g) and concentrated. Isopropyl alcohol (80 g) was added to the obtained crude product, and recrystallization yielded 16.9 g of [MA-3-3].

[0179] A 1 L four-neck flask was charged with [MA-3-3] (16.9 g, 36 mmol) and formic acid (170 g) and stirred at 50 °C. After the reaction was completed, the reaction solution was poured into pure water (2000 g) and the precipitate was filtered off. Acetonitrile (400 g) was added to the obtained crude product and heated to 60 °C to dissolve it. After removing the insoluble matter, the mixture was concentrated. Ethyl acetate (40 g) and hexane (400 g) were further added to the crude product and repulped and washed at room temperature to obtain 8.1 g of [MA-3-4].

[0180] A 200 mL four-neck flask was charged with [MA-3-4] (7.8 g, 19 mmol), oxalyl chloride (2.7 g, 21 mmol), DMF (a few drops), and THF (60 g) and reacted at 0 °C for 2 h. Subsequently, the resulting chloroformate was added dropwise to a reaction solution containing 2-hydroxyethyl methacrylate (2.7 g, 21 mmol), pyridine (2.1 g, 27 mmol), and THF (23 g) in an ice bath and stirred at 50 °C. After completion of the reaction, the reaction system was poured into ethyl acetate (500 g), and the organic layer was washed with purified water (1500 g) and concentrated. The resulting crude material was subjected to origin cut with silica gel using an ethyl acetate / hexane (volume ratio 1:5). Hexane (50 g) was added to the crude material and heated to 50 °C to dissolve it. After removing insoluble material, the mixture was concentrated. Next, methanol (60 g) was added to the crude product, and recrystallization was carried out at −20° C. to obtain 1.3 g of [MA-3] (white solid). 1 The results of H-NMR are shown below, and it was confirmed that the obtained solid was the desired [MA-3]. 1 H NMR (500 MHz, [D6]-DMSO):δ8.21-8.22 (d,2H), 7.85-7.87 (d,2H), 7.70-7.74 (d,1H), 7.36-7.41 (m,4H), 6.68-6.71 (d,1H), 6.05 (s,1H), 5.71 (s,1H), 4.43-4.44 (m,2H), 4.37-4.39 (m,2H), 2.93-2.96 (t,2H), 2.67-2.74 (m,2H), 1.89 (s,3H)

[0181] (Monomer Synthesis Example 4) Synthesis of [MA-4]:

[0182] [ka]

[0183] A 1 L four-neck flask was charged with [MA-1-1] (20.0 g, 66 mmol), 3,3,3-trifluoropropionic acid (9.5 g, 74 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (19.4 g, 101 mmol), 4-dimethylaminopyridine (0.8 g, 7 mmol), and THF (200 g) and stirred at room temperature. After completion of the reaction, the reaction solution was poured into purified water (1000 g), and the precipitate was filtered off. Ethyl acetate (300 g) was added to the resulting crude product to completely dissolve it, and the organic layer was washed with purified water (1500 g) and concentrated. Ethyl acetate (100 g) and hexane (500 g) were added to the resulting crude product, and the mixture was repulped and washed at 0 °C to obtain 23.9 g of [MA-4-1].

[0184] A 1 L four-neck flask was charged with [MA-4-1] (23.9 g, 58 mmol) and formic acid (240 g) and stirred at 50 °C. After the reaction was completed, the reaction solution was poured into pure water (1000 g) and the precipitate was filtered off. Ethyl acetate (1000 g) was added to the obtained crude product to completely dissolve it, and the organic layer was washed with pure water (1500 g) and concentrated. Hexane (40 g) was added to the obtained crude product and repulp washed at 0 °C to obtain 19.6 g of [MA-4-2].

[0185] A 500 mL four-neck flask was charged with [MA-4-2] (19.6 g, 55 mmol), 2-hydroxyethyl methacrylate (7.9 g, 61 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (15.8 g, 83 mmol), 4-dimethylaminopyridine (0.7 g, 6 mmol), and THF (200 g), and the mixture was stirred at room temperature. After the reaction was completed, the reaction solution was poured into ethyl acetate (600 g), and the organic layer was washed with purified water (1500 g) and concentrated. The resulting crude product was subjected to origin cut with silica gel using an ethyl acetate / hexane (volume ratio 1:3). Hexane (200 g) was then added to the resulting crude product, and the mixture was repulped and washed at room temperature, yielding 23.6 g of [MA-4] (white solid). 1 The results of H-NMR are shown below, and it was confirmed that the obtained solid was the desired [MA-4]. 1 H NMR (500 MHz, [D6]-DMSO):δ7.62-7.65 (m,3H), 7.30-7.31 (d,2H), 6.59-6.62 (d,1H), 6.04 (s,1H), 5.70 (s,1H), 4.80-4.84 (m,1H), 4.40-4.42 (m,2H), 4.36-4.38 (m,2H), 3.64-3.70 (m,2H) 2.56-2.61 (m,1H), 2.01-2.04 (d,2H), 1.88 (s,3H), 1.82-1.85 (d,2H), 1.58-1.66 (m,2H), 1.50-1.55 (m,2H)

[0186] (Monomer Synthesis Example 5) Synthesis of [MA-5]:

[0187] [ka]

[0188] A 1 L four-neck flask was charged with [MA-1-1] (20.0 g, 66 mmol), trifluoroacetic acid (8.4 g, 74 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (19.4 g, 101 mmol), 4-dimethylaminopyridine (0.8 g, 7 mmol), and THF (200 g) and stirred at room temperature. After completion of the reaction, the reaction solution was poured into purified water (1000 g), and the precipitate was filtered off. Ethyl acetate (300 g) was added to the resulting crude product to completely dissolve it, and the organic layer was washed with purified water (900 g) and concentrated. The resulting crude product was purified with an ethyl acetate / hexane (volume ratio 1:4) solution and subjected to origin cut with silica gel to obtain 20.7 g of [MA-5-1].

[0189] A 1 L four-neck flask was charged with [MA-5-1] (20.7 g, 52 mmol) and formic acid (210 g) and stirred at 50 °C. After the reaction was completed, the reaction solution was poured into pure water (1000 g) and the precipitate was filtered off. Methanol (600 g) was added to the obtained crude product to completely dissolve it, and then the mixture was concentrated. Ethyl acetate (500 g) was added to the obtained crude product, and the mixture was repulped and washed at room temperature to obtain 16.5 g of [MA-5-2].

[0190] A 500 mL four-neck flask was charged with [MA-5-2] (16.5 g, 48 mmol), 2-hydroxyethyl methacrylate (6.9 g, 53 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (15.7 g, 82 mmol), 4-dimethylaminopyridine (0.88 g, 7 mmol), and THF (170 g), and the mixture was stirred at room temperature. After the reaction was completed, the reaction solution was poured into ethyl acetate (600 g), and the organic layer was washed with purified water (1500 g) and concentrated. The resulting crude product was subjected to origin cut with silica gel using an ethyl acetate / hexane (volume ratio 1:3). Hexane (150 g) was then added to the resulting crude product, and the mixture was repulped and washed at room temperature, yielding 13.3 g of [MA-5] (white solid). 1 The results of H-NMR are shown below, and it was confirmed that the obtained solid was the desired [MA-5]. 1 H NMR (500 MHz, [D6]-DMSO):δ7.63-7.66 (m,3H), 7.30-7.32 (d,2H), 6.60-6.63 (d,1H), 6.04 (s,1H), 5.70 (s,1H), 5.04-5.05 (m,1H), 4.40-4.42 (m,2H), 4.36-4.38 (m,2H), 2.62-2.63 (m,1H), 2.12-2.14 (d,2H), 1.88 (s,3H), 1.86-1.87 (d,2H), 1.61-1.68 (m,4H)

[0191] (Monomer Synthesis Example 6) Synthesis of [MA-6]:

[0192] [ka]

[0193] A 1-L four-neck flask was charged with trans-4-hydroxycyclohexanecarboxylic acid (48.9 g, 339 mmol), triethylamine (34.6 g, 342 mmol), and THF (391 g), and chloromethyl methyl ether (28.7 g, 356 mmol) was added dropwise under ice-cooled conditions in a nitrogen atmosphere. After the dropwise addition, the mixture was allowed to react at room temperature for 3 hours to remove the raw materials. After the reaction was completed, the precipitate was removed by filtration, and the solvent was removed by concentration under reduced pressure. The resulting oily compound was diluted with ethyl acetate (490 g), and the ethyl acetate solution was washed three times with pure water (250 g). The ethyl acetate solution was then dehydrated over magnesium sulfate and concentrated under reduced pressure to obtain 49.6 g of [MA-6-1].

[0194] A 1 L four-neck flask was charged with [MA-6-1] (25.3 g, 134 mmol), 4,4,4-trifluorobutyric acid (20.0 g, 141 mmol), 4-dimethylaminopyridine (1.64 g, 13.4 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (31.0 g, 162 mmol), and THF (126 g), and the mixture was reacted at room temperature for 15 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate (500 g), and the ethyl acetate solution was washed four times with purified water (250 g). The organic phase was concentrated under reduced pressure to yield 41.8 g of [MA-6-2].

[0195] A 1 L four-neck flask was charged with [MA-6-2] (41.8 g, 134 mmol), 4 mol / L hydrochloric acid aqueous solution (82.0 mL), and acetonitrile (204 g), and the mixture was heated to 45 °C for 4 hours. After the reaction was completed, the acetonitrile was removed by vacuum concentration, and purified water (480 g) was added to precipitate crystals. The precipitated crystals were collected by filtration and washed with a slurry of toluene (80.0 g) and hexane (120 g). The slurry solution was filtered, and the obtained crystals were dried to obtain 15.8 g of [MA-6-3].

[0196] A 500 mL four-neck flask was charged with [MA-6-3] (15.8 g, 58 mmol), trans-p-tert-butyl coumarate (15.7 g, 71 mmol), 4-dimethylaminopyridine (0.7 g, 5 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (13.4 g, 70 mmol), and CHCl2 (160 g) and reacted at room temperature for 5 hours. After completion of the reaction, the reaction mixture was diluted with methylene chloride (320 g), and the organic phase was washed three times with purified water (300 g). The organic phase was dehydrated over magnesium sulfate and concentrated under reduced pressure to obtain a crude product. The crude product was slurry-washed with hexane (300 g), filtered, and dried to obtain 23.8 g of [MA-6-4].

[0197] A 500 mL four-neck flask was charged with [MA-6-4] (23.8 g, 51 mmol) and formic acid (240 g) and reacted for 5 hours at 60 °C. After the reaction was completed, the reaction solution was poured into pure water (720 g) to precipitate crystals, which were then filtered and washed with pure water to obtain a crude product. The crude product was recrystallized in a tetrahydrofuran (48 g) / acetonitrile (192 g) mixed solvent, filtered, and dried to obtain 14.2 g of [MA-6-5].

[0198] A 500 mL four-neck flask was charged with [MA-6-5] (14.2 g, 34.3 mmol), 2-hydroxyethyl methacrylate (5.4 g, 418 mmol), 4-dimethylaminopyridine (0.4 g, 3 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (9.3 g, 49 mmol), and THF (127 g), and the mixture was allowed to react at room temperature for approximately 1 day. After the reaction was completed, the tetrahydrofuran solution was recovered by decantation, and the tetrahydrofuran was removed by vacuum concentration. The concentrate was diluted with ethyl acetate (500 g), washed three times with pure water (200 g), and then dehydrated using magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure, and the concentrate was purified on a silica gel column using an ethyl acetate / hexane (volume ratio 1:6 → 1:5) solution, yielding 12.8 g of [MA-6-5] (white crystals). 1 The results of H-NMR are shown below, and it was confirmed that the obtained solid was the desired [MA-6]. 1 H NMR (500 MHz, [D6]-DMSO):δ7.80 (d,2H), 7.69 (d,1H), 7.18 (d,2H), 6.66 (d,1H), 6.05 (s,1H), 5.70 (s,1H), 4.68-4.74 (m,1H), 4.42-4.43 (m,2H), 4.29-4.38 (m,2H), 2.64-2.69 (m,1H), 2.52-2.63 (m,4H), 2.09-2.12 (m,2H), 1.96-1.99 (m,2H), 1.88 (s,3H), 1.58-1.66 (m,2H), 1.44-1.52 (m,2H)

[0199] (Monomer Synthesis Example 7) Synthesis of [MA-7]:

[0200] [ka]

[0201] A 500 mL four-neck flask was charged with [MA-1-1] (20.0 g, 66 mmol), butyric acid (6.4 g, 73 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (19.0 g, 99 mmol), 4-dimethylaminopyridine (0.8 g, 7 mmol), and THF (200 g) and stirred at room temperature. After completion of the reaction, the reaction solution was poured into ethyl acetate (1000 g), and the organic layer was washed with purified water (1500 g) and concentrated. Hexane (100 g) was added to the resulting crude product, which was then repulped and washed at 0 °C to obtain 20.1 g of [MA-7-1].

[0202] A 500 mL four-neck flask was charged with [MA-7-1] (20.1 g, 54 mmol) and formic acid (200 g) and stirred at 50°C. After the reaction was completed, the reaction solution was poured into pure water (1000 g) and the precipitate was filtered off. Ethyl acetate (800 g) was added to the obtained crude product to completely dissolve it, and the organic layer was washed with pure water (1000 g) and concentrated. Ethyl acetate (50 g) was added to the obtained crude product and repulp washed at 0°C, yielding 16.2 g of [MA-7-2].

[0203] A 500 mL four-neck flask was charged with [MA-7-2] (16.2 g, 51 mmol), 2-hydroxyethyl methacrylate (7.3 g, 56 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (14.7 g, 77 mmol), 4-dimethylaminopyridine (0.62 g, 5 mmol), and THF (160 g), and the mixture was stirred at room temperature. After the reaction was completed, the reaction solution was poured into ethyl acetate (1000 g), and the organic layer was washed with purified water (1500 g) and concentrated. The resulting crude product was subjected to origin cut with silica gel using an ethyl acetate / hexane (volume ratio 1:5). Hexane (300 g) was then added to the resulting crude product, and the mixture was repulped and washed at 0°C, yielding 18.4 g of [MA-7] (white solid). 1 The results of H-NMR are shown below, and it was confirmed that the obtained solid was the desired [MA-7]. 1 H NMR (500 MHz, [D6]-DMSO):δ7.62-7.65 (m,3H), 7.29-7.31 (d,2H), 6.59-6.62 (d,1H), 6.04 (s,1H), 5.70 (s,1H), 4.70-4.73 (m,1H), 4.40-4.42 (m,2H), 4.36-4.38 (m,2H), 2.55-2.58 (m,1H), 2.24-2.27 (t,2H), 1.98-2.00 (d,2H), 1.88 (s,3H), 1.81-1.83 (d,2H), 1.56-1.61 (m,4H), 1.46-1.54 (m,2H), 0.87-0.90 (t,3H)

[0204] <Methacrylate polymer synthesis example 1> MA-1 (3.86 g, 8.00 mmol), GMA (0.56 g, 4.00 mmol), and MAA (0.69 g, 8.00 mmol) were dissolved in NMP (29.9 g), and the solution was degassed using a diaphragm pump. AIBN (0.16 g, 0.5 mmol) was added as a polymerization initiator, and the solution was degassed again. The mixture was then reacted at 60°C for 13 hours to obtain a polymer solution. Next, NMP (5.0 g) and BCS (6.0 g) were added to this polymer solution (4.0 g) and stirred at room temperature to obtain a methacrylate polymer solution (MP1). The number average molecular weight of this polymer was 34,000 and the weight average molecular weight was 120,000.

[0205] <Methacrylate polymer synthesis example 2> MA-1 (3.86 g, 8.00 mmol) and MAA (1.03 g, 12.00 mmol) were dissolved in NMP (28.7 g), and the solution was degassed using a diaphragm pump. AIBN (0.16 g, 0.5 mmol) was added as a polymerization initiator, and the solution was degassed again. The mixture was then reacted at 60°C for 13 hours to obtain a polymer solution. Next, NMP (5.0 g) and BCS (6.0 g) were added to this polymer solution (4.0 g) and stirred at room temperature to obtain a methacrylate polymer solution (MP2). The number average molecular weight of this polymer was 44,000 and the weight average molecular weight was 140,000.

[0206] <Methacrylate polymer synthesis example 3> MA-1 (3.86 g, 8.00 mmol) and MOI-BP (3.02 g, 12.00 mmol) were dissolved in NMP (36.7 g), and the solution was degassed using a diaphragm pump. AIBN (0.16 g, 0.5 mmol) was added as a polymerization initiator, and the solution was degassed again. The mixture was then reacted at 60°C for 13 hours to obtain a polymer solution. Next, NMP (5.0 g) and BCS (6.0 g) were added to this polymer solution (4.0 g) and stirred at room temperature to obtain a methacrylate polymer solution (MP3). The number average molecular weight of this polymer was 45,000 and the weight average molecular weight was 145,000.

[0207] <Methacrylate Polymer Synthesis Examples 4 to 13> Using the compositions shown in Table 1, methacrylate polymer solutions (MP4) to (MP13) were synthesized using the same methods as in Methacrylate Polymer Synthesis Examples 1 to 3.

[0208] [Table 1]

[0209] <Polyamic Acid Polymer Synthesis Example 1> B1 (1.14 g, 3.00 mmol), C2 (0.61 g, 4.00 mmol), C7 (0.73 g, 3.00 mmol), and A1 (1.12 g, 6.00 mmol) were dissolved in NMP (13.6 g) and reacted at 60°C for 5 hours. After that, A2 (0.50 g, 2.00 mmol), A4 (0.44 g, 2.00 mmol), and NMP (4.6 g) were added, and the mixture was reacted at 40°C for 10 hours to obtain a polyamic acid polymer solution (MP14).

[0210] <Polyamic Acid Polymer Synthesis Examples 2 to 17> Using the compositions shown in Table 2 and the same method as in Polyamic Acid Polymer Synthesis Example 1, polyamic acid polymer solutions (MP15) to (MP30) were synthesized.

[0211] [Table 2]

[0212] <Polyimide polymer synthesis example 1> NMP was added to 50 g of the polyamic acid polymer solution (MP14) to dilute it to 6.5% by mass, and then 8.8 g of acetic anhydride and 2.7 g of pyridine were added as imidization catalysts and the mixture was allowed to react at 75°C for 2.5 hours. The reaction solution was poured into 700 ml of methanol, and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100°C to obtain polyimide polymer powder (E). The imidization rate of this polyimide polymer was 71%, and the number average molecular weight was 13,000 and the weight average molecular weight was 42,000.

[0213] NMP (44.0 g) was added to the obtained polyimide powder (E) (6.0 g), and the mixture was dissolved by stirring at 70° C. for 20 hours. NMP (10.0 g) and BCS (40.0 g) were added to this solution, and the mixture was stirred at room temperature for 5 hours to obtain a polyimide polymer solution (MP31).

[0214] <Polyimide Polymer Synthesis Examples 2-17> Using the polyamic acid polymer solutions obtained in Polyamic Acid Polymer Synthesis Examples 2 to 17, polyimide polymer solutions (MP32) to (MP47) were synthesized in the same manner as in Polyimide Polymer Synthesis Example 1.

[0215] Example 1 To the methacrylate polymer solution (MP1) (4.0 g) obtained in Methacrylate Polymer Synthesis Example 1, crosslinking agent (D3) (0.06 g) was added and stirred at room temperature to obtain a liquid crystal alignment agent (PM1).

[0216] (Examples 2 and 3) The methacrylate polymer solutions (MP2) to (MP3) obtained in Methacrylate Polymer Synthesis Examples 2 and 3 were used in the same manner as in Example 1 to obtain liquid crystal alignment agents (PM2) and (PM3).

[0217] Example 4 To the methacrylate polymer solution (MP1) (3.0 g) obtained in Methacrylate Polymer Synthesis Example 1, a solution (7.0 g) prepared by adding NMP and BCS to the polyamic acid polymer solution (MP14) obtained in Polyamic Acid Polymer Synthesis Example 1 to give a polyamic acid polymer:NMP:BCS=4:56:40 (mass ratio) was added, and then a crosslinker (D3) (0.06 g) was added and stirred at room temperature to obtain a liquid crystal alignment treatment agent (PM4).

[0218] Examples 5 to 20 The same operation as in Example 4 was carried out using the methacrylate polymer solution (MP1), the polyamic acid polymer solutions (MP15) to (MP30), and the crosslinking agent (D3) to obtain liquid crystal alignment treatment agents (PM5) to (PM20). The compositions of the liquid crystal alignment treatment agents (PM5) to (PM20) are shown in Table 3.

[0219] Example 21 To the methacrylate polymer solution (MP1) (3.0 g) obtained in Methacrylate Polymer Synthesis Example 1, the polyimide polymer solution (MP31) (7.0 g) obtained in Polyimide Polymer Synthesis Example 1 was added, and then the crosslinking agent (D3) (0.06 g) was added, and the mixture was stirred at room temperature to obtain a liquid crystal alignment treatment agent (PM21).

[0220] (Examples 22 to 48) The same operation as in Example 21 was carried out using methacrylate polymer solutions (MP1) to (MP10), polyimide polymer solutions (MP31) to (MP47), and crosslinking agents (D1) to (D3), to obtain liquid crystal alignment treatment agents (PM22) to (PM48). The compositions of liquid crystal alignment treatment agents (PM22) to (PM48) are shown in Table 3.

[0221] [Table 3]

[0222] (Comparative Example 1) To the polymer solution (MP11) (4.0 g) obtained in Methacrylate Polymer Synthesis Example 11, crosslinking agent (D3) (0.06 g) was added and stirred at room temperature to obtain a liquid crystal alignment agent (RPM1).

[0223] (Comparative Example 2, Comparative Example 3) The polymer solutions obtained in Methacrylate Polymer Synthesis Examples 12 and 13 were used in the same manner as in Comparative Example 1 to obtain liquid crystal alignment agents (RPM2) and (RPM3).

[0224] Comparative Example 4 To the methacrylate polymer solution (MP11) (3.0 g) obtained in Methacrylate Polymer Synthesis Example 11, a solution (7.0 g) prepared by adding NMP and BCS to the polyamic acid polymer solution (MP14) obtained in Polyamic Acid Polymer Synthesis Example 1 to give a polyamic acid polymer:NMP:BCS=4:56:40 (mass ratio) was added, and then a crosslinker (D3) (0.06 g) was added and stirred at room temperature to obtain a liquid crystal alignment treatment agent (RPM4).

[0225] (Comparative Examples 5 and 6) The methacrylate polymer solutions obtained in Methacrylate Polymer Synthesis Examples 12 and 13 were treated in the same manner as in Comparative Example 4 to obtain liquid crystal alignment agents (RPM5) and (RPM6). (Comparative Example 7) To the methacrylate polymer solution (MP11) (3.0 g) obtained in Methacrylate Polymer Synthesis Example 11, the polyimide polymer solution (MP31) (7.0 g) obtained in Polyimide Polymer Synthesis Example 1 was added, and then the crosslinking agent (D3) (0.06 g) was added, and the mixture was stirred at room temperature to obtain a liquid crystal alignment treatment agent (RPM7).

[0226] (Comparative Examples 8 and 9) Using the methacrylate polymer solutions obtained in Methacrylate Polymer Synthesis Examples 12 and 13, liquid crystal alignment agents (RPM8) and (RPM9) were obtained in the same manner as in Comparative Example 7.

[0227] <Fabrication of Liquid Crystal Display Element> The liquid crystal alignment treatment agents (PM1) to (PM48) obtained in the examples and the liquid crystal alignment treatment agents (RPM1) to (RPM9) obtained in the comparative examples were pressure filtered through a membrane filter with a pore size of 1 μm. The obtained solution was spin-coated onto the ITO surface of a glass substrate with a transparent electrode made of ITO film, dried on a hot plate at 70°C for 90 seconds, and then baked on a hot plate at 200°C for 30 minutes to form a liquid crystal alignment film with a thickness of 100 nm. Next, the coating surface was irradiated with a polarizing plate at an intensity of 4.3 mW / cm 2 313 nm linearly polarized ultraviolet light at an angle of 40° from the substrate normal direction, 50 mJ / cm 2 The linearly polarized ultraviolet light was prepared by passing ultraviolet light from a high-pressure mercury lamp through a 313 nm bandpass filter and then through a 313 nm polarizing plate. Two of the above substrates were prepared. Four-micrometer bead spacers were dispersed on the liquid crystal alignment film of one substrate, and then a sealant (Mitsui Chemicals, XN-1500T) was applied. The other substrate was then attached so that the liquid crystal alignment film faces each other and the alignment direction was 180°. The sealant was then thermally cured at 120°C for 90 minutes to produce an empty cell. Liquid crystal (Merck, MLC-3022) was injected into this empty cell using a vacuum injection method, resulting in a liquid crystal display device.

[0228] <Evaluation> (liquid crystal alignment) The liquid crystal display element obtained above was subjected to isotropic phase treatment at 120°C for 1 hour, and then the cell was observed under a polarizing microscope. A good result was determined if there were no alignment defects such as light leakage or domain generation, or if uniform liquid crystal drive was obtained when voltage was applied to the liquid crystal cell. The evaluation results are shown in Table 4.

[0229] (pretilt angle) The pretilt angle of the liquid crystal cell of the liquid crystal display element prepared above was measured by the Mueller matrix method using an AxoScan manufactured by Axo Metrix Co., Ltd. The evaluation results are shown in Table 4.

[0230] (Evaluation of tilt angle change) After measuring the pretilt angle, AC 15Vp-p was applied to the liquid crystal cell, and the tilt angle was measured again after 36 hours to calculate how much the tilt angle had changed. The evaluation results are shown in Table 4.

[0231] [Table 4]

[0232] As can be seen from the results in Table 4, comparing Examples 1 to 46 with Comparative Examples 1 to 9, a polymethacrylate solution containing a photo-aligning monomer that does not have -COO- or -OCO- in R3 in formula (pa-1), or a blend of such a polymethacrylate solution with a polyamic acid or polyimide solution, had low tilt angle stability (large change in tilt angle), whereas a polymethacrylate solution containing a photo-aligning monomer that has -COO- or -OCO- in R3 in formula (pa-1), or a blend of such a polymethacrylate solution with a polyamic acid or polyimide solution, provided a liquid crystal alignment film with high tilt angle stability (small change in tilt angle). [Industrial Applicability]

[0233] The liquid crystal aligning agent of the present invention and the liquid crystal display element using the liquid crystal alignment film obtained therefrom can be suitably used as a liquid crystal display element that requires durability, such as for use in a vehicle.< / x> < / x>

Claims

1. The following formula (MA) (wherein, S b represents a linear alkyl group having 2 carbon atoms, and R ６ is a hydrogen atom or a methyl group, and R ７ is a single bond or —OCO—, and R ８ is a divalent aromatic group or a divalent alicyclic group, and R ９ is -OCO-, and R １０ is a linear alkyl group having 1, 2 or 3 carbon atoms, in which a hydrogen atom of the alkyl group may be substituted with a fluorine atom, and b is 1. 【Chemical 1】

2. A polymerizable monomer having a photoalignable group represented by any one of the following formulae (MA-1) to (MA-7): 【Chemistry 2】

3. The following formula (MA) (wherein, S b represents a linear alkyl group having 2 carbon atoms, and R ６ is a hydrogen atom or a methyl group, and R ７ is a single bond or —OCO—, and R ８ is a divalent aromatic group or a divalent alicyclic group, and R ９ is -OCO-, and R １０ is a linear alkyl group having 1, 2 or 3 carbon atoms, in which a hydrogen atom of the alkyl group may be substituted with a fluorine atom, and b is 1. 【Chemistry 3】

4. The polymer according to claim 3, wherein the monomer represented by formula (MA) is a polymerizable monomer represented by any one selected from the group consisting of formulas (MA-1) to (MA-7): 【Chemistry 4】

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