Composition for forming cured film, alignment material, and phase-difference material

Abstract

[PROBLEM] To provide a composition for forming a cured film having excellent solvent resistance and that is capable of aligning polymerizable liquid crystals with high sensitivity, and that is used for forming an alignment material with minimal liquid crystal variation. [SOLUTION] Provided is a composition for forming a cured film contains (A) a compound having a photo-aligning group, (B) a polymer having a structural unit that has an N-hydroxymethyl group or an N-alkoxymethyl group, and (C) a cyclodextrin derivative in which some or all hydroxy groups are modified. Further provided are an alignment material and a phase difference material.

Description

Cured film-forming composition, alignment material, and retardation material

[0001] The present invention relates to a cured film-forming composition, an alignment material, and a retardation material.

[0002] In the case of a 3D display using circularly polarized glasses, a retardation material is usually disposed on a display element that forms an image, such as a liquid crystal panel. This retardation material has two types of retardation regions with different retardation characteristics, each of which is regularly arranged in a plurality of regions, forming a patterned retardation material. In the following description, such a retardation material that is patterned so as to arrange a plurality of retardation regions with different retardation characteristics is referred to as a patterned retardation material.

[0003] A patterned retardation material can be produced by optically patterning a retardation material made of polymerizable liquid crystal, as disclosed in, for example, Patent Document 1. Optical patterning of a retardation material made of polymerizable liquid crystal utilizes photo-alignment technology known for forming alignment materials for liquid crystal panels. That is, a coating film made of a photo-alignable material is provided on a substrate, and two types of polarized light with different polarization directions are irradiated onto the coating. A photo-alignment film is then obtained as an alignment material in which two types of liquid crystal alignment regions with different liquid crystal alignment control directions are formed. A solution-like retardation material containing polymerizable liquid crystal is applied onto this photo-alignment film to achieve alignment of the polymerizable liquid crystal. The aligned polymerizable liquid crystal is then cured to form a patterned retardation material.

[0004] The anti-reflection film of an organic EL display is composed of a linear polarizer and a quarter-wave retardation plate. External light directed toward the panel surface of the image display panel is converted into linearly polarized light by the linear polarizer, and then converted into circularly polarized light by the subsequent quarter-wave retardation plate. This circularly polarized external light is reflected by the surface of the image display panel, but the direction of rotation of the polarization plane is reversed upon reflection. As a result, this reflected light is converted by the quarter-wave retardation plate into linearly polarized light in the direction that is blocked by the linear polarizer, in the opposite direction to when it arrived, and is then blocked by the subsequent linear polarizer, resulting in significant suppression of external emission.

[0005] Regarding this quarter-wave retardation plate, Patent Document 2 proposes a method of constructing this optical film with reverse dispersion characteristics by combining a half-wave plate and a quarter-wave plate to form a quarter-wave retardation plate. In this method, an optical film with reverse dispersion characteristics can be constructed using a liquid crystal material with positive dispersion characteristics in a wide wavelength band used for displaying color images.

[0006] In recent years, liquid crystal materials applicable to the retardation layer have been proposed that have reverse dispersion characteristics (Patent Documents 3 and 4). With such liquid crystal materials with reverse dispersion characteristics, instead of combining a half-wave plate and a quarter-wave plate to form a quarter-wave retardation plate using two retardation layers, the retardation layer can be formed as a single layer to ensure reverse dispersion characteristics, thereby enabling an optical film that can ensure a desired retardation over a wide wavelength band to be realized with a simple configuration.

[0007] An alignment layer is used to align liquid crystals. Known methods for forming alignment layers include rubbing and photo-alignment. Photo-alignment is advantageous in that it does not generate static electricity or dust, which are problems with rubbing, and allows for quantitative control of the alignment process.

[0008] In forming alignment materials using a photoalignment method, acrylic resins and polyimide resins having photodimerization moieties such as cinnamoyl groups and chalcone groups in the side chains are known as usable photoalignment materials. These resins have been reported to exhibit the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) when irradiated with polarized UV light (see Patent Documents 5 to 7).

[0009] Furthermore, there are also examples in which a thermal crosslinking system is introduced into a photoalignment agent using a cinnamoyl moiety in order to improve alignment sensitivity and impart solvent resistance (see Patent Documents 8 and 9).

[0010] Japanese Patent Application Publication No. 2005-49865, Japanese Patent Application Publication No. 10-68816, U.S. Patent No. 8,119,026, Japanese Patent Application Publication No. 2009-179563, Japanese Patent No. 3,611,342, Japanese Patent Application Publication No. 2009-058584, Japanese Patent Publication No. 2001-517719, International Patent Application Publication No. WO2011 / 126022, International Patent Application Publication No. WO2014 / 010688

[0011] When manufacturing a retardation material using photo-alignment technology, in recent years, in response to the demand for reducing manufacturing costs, the production of optical materials by the so-called roll-to-roll method is required on inexpensive resin films such as acrylic film, TAC (triacetyl cellulose) film, and COP (cycloolefin polymer) film, and in particular, due to its excellent optical properties and reliability and the advantage of being able to reduce manufacturing costs, it is required to use acrylic film as the resin film (substrate). However, in the photo-alignment film formed from the conventional materials as described above, there is a problem that the solvent resistance of the alignment film is low, so that parts that repel liquid crystal, so-called repelling, occur, and alignment defects occur.

[0012] The present invention has been made based on the above findings and study results. That is, an object of the present invention is to provide a cured film-forming composition for forming a cured film used to form an alignment material that has excellent solvent resistance, is capable of aligning a polymerizable liquid crystal with high sensitivity, and is less likely to repel water.

[0013] Another object of the present invention is to provide an alignment material and a retardation material formed using the above cured film.

[0014] Other objects and advantages of the present invention will become apparent from the following description.

[0015] As a result of extensive research into achieving the above object, the present inventors have discovered that the inclusion of a cyclodextrin derivative in which some or all of the hydroxy groups have been modified can suppress repelling of liquid crystals, and have completed the present invention, which has the following gist:

[0016] That is, the present invention encompasses the following: [1] A cured film-forming composition comprising: (A) a compound having a photoalignable group; (B) a polymer having a structural unit having an N-hydroxymethyl group or an N-alkoxymethyl group; and (C) a cyclodextrin derivative in which some or all of the hydroxy groups have been modified. [2] The cured film-forming composition according to [1] above, wherein the photoalignable group of component (A) is a functional group having a structure that undergoes photodimerization or photoisomerization. [3] The cured film-forming composition according to [1] above, wherein the photoalignable group of component (A) is a cinnamoyl group. [4] The cured film-forming composition according to [1] above, wherein the photoalignable group of component (A) is a group having an azobenzene structure. [5] The cured film-forming composition according to [1] above, wherein component (B) is a polymer further having a structural unit having a partial structure represented by the following formula (1): (In formula (1), Q １ represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group; Q ２ is O, S or NQ ３ represents Q ３ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the dashed line represents a bond.) [6] The cured film-forming composition according to the above item [1], further comprising a crosslinking catalyst as a component (D). [7] The cured film-forming composition according to the above item [1], further comprising an adhesion improving component as a component (E). [8] An alignment material obtained using the cured film-forming composition according to any one of the above items [1] to [7]. [9] A retardation material formed using a cured film obtained from the cured film-forming composition according to any one of the above items [1] to [7].

[0017] According to the present invention, it is possible to provide a cured film-forming composition that has excellent solvent resistance, can align polymerizable liquid crystals with high sensitivity, and can form a cured film that provides an alignment material with little liquid crystal cissing. Furthermore, according to the present invention, it is possible to provide an optical film having the above-mentioned cured film, and an alignment material and a retardation material formed using the cured film or the optical film. The mechanism by which the above-mentioned effects of the present invention are achieved is not necessarily clear, but the following is thought to be one of the reasons. The cyclodextrin derivative of component (C) has high solvent resistance to liquid crystal solvents, making it easy to maintain the anisotropy of the alignment component and reducing the amount of eluate that causes cissing. In addition, it is thought that the surface hydrophilization by the cyclodextrin improves the leveling ability of the liquid crystal.

[0018] The present invention will be described in detail below. Note that the following explanation of the constituent elements is an example for explaining the present invention, and the present invention is not limited to these contents.

[0019] <Cured Film-Forming Composition> The cured film-forming composition of the present invention is a cured film-forming composition comprising (A) a compound having a photoalignable group, (B) a polymer having a structural unit having an N-hydroxymethyl group or an N-alkoxymethyl group and a structural unit having a partial structure represented by formula (1), and (C) a cyclodextrin derivative in which some or all of the hydroxy groups have been modified. Each component will be described in detail below.

[0020] [Component (A)] The component (A) in the cured film-forming composition of the present invention is a compound having a photoalignable group, more specifically, a low molecular weight compound or polymer having a photoalignable group and a thermally crosslinkable group. That is, the component (A) is a component that imparts photoalignment properties to a cured film obtained from the cured film-forming composition of the present invention, and in this specification, the component (A) is also referred to as a photoalignment component.

[0021] <Low Molecular Weight Compound Having a Photo-Alignment Group and a Thermally Crosslinkable Group> In the cured film-forming composition of the present invention, the low molecular weight compound of component (A) is a compound having a photo-alignment group, and may be a compound further having one group selected from the group consisting of a hydroxy group, a carboxy group, an amide group, an amino group, and an alkoxysilyl group. In the present invention, the photo-alignment group generally refers to a functional group that exhibits the property of being aligned by light irradiation, and typically refers to a functional group at a structural site that undergoes photodimerization or photoisomerization. Other photo-alignment groups include, for example, functional groups that undergo a photo-Fries rearrangement reaction (e.g., benzoic acid ester compounds) and groups that undergo a photodecomposition reaction (e.g., cyclobutane rings).

[0022] The photodimerizable structural moiety that the low molecular weight compound of component (A) can have as a photoalignment group is a moiety that forms a dimer upon irradiation with light, and specific examples thereof include a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, etc. Among these, a cinnamoyl group is preferred because of its high transparency in the visible light region and its high photodimerization reactivity.

[0023] Furthermore, the photoisomerizable structural moiety that the low molecular weight compound of component (A) can have as a photoalignment group refers to a structural moiety that changes between a cis form and a trans form upon irradiation with light, and specific examples thereof include moieties consisting of an azobenzene structure, a stilbene structure, etc. Among these, an azobenzene structure is preferred due to its high reactivity.

[0024] The low molecular weight compound having a photoalignable group and one group selected from the group consisting of a hydroxy group, a carboxy group, an amide group, an amino group, and an alkoxysilyl group is, for example, a compound represented by the following formula:

[0025]

[0026] In the above formula, A １ and A ２ each independently represents a hydrogen atom or a methyl group.

[0027] X １１represents a structure in which 1 to 3 substituents selected from alkylene groups having 1 to 18 carbon atoms, phenylene groups, biphenylene groups, and combinations thereof are bonded via one or more bonds selected from a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, a carbonyl bond, and combinations thereof, and the structure may be such that a plurality of the substituents are linked via the bonds.

[0028] X １２ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded to two or more groups via a single bond, an ether bond, an ester bond, an amide bond, or a urea bond.

[0029] X １３ represents a hydroxy group, a mercapto group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a phenoxy group, a biphenyloxy group, or a phenyl group.

[0030] X １４ represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear.

[0031] X １５ represents a hydroxy group, a carboxy group, an amide group, an amino group, or an alkoxysilyl group, provided that X １４ When is a single bond, X １５ is a hydroxy group or an amino group.

[0032] X represents a single bond, an oxygen atom, or a sulfur atom. １４ is a single bond, then X is also a single bond.

[0033] When these substituents contain a benzene ring, a hydrogen atom on the benzene ring may be substituted with one or more identical or different substituents selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group, and a cyano group.

[0034] In the above formula, R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group, or a cyano group.

[0035] Specific examples of the low molecular weight compound having a photoalignable group and a hydroxy group, which is the component (A), include the compounds represented by the above formulas [A11] to [A15], and compounds other than those represented by the formulas, such as 4-(8-hydroxyoctyloxy)cinnamic acid methyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid methyl ester, 4-(4-hydroxybutyloxy)cinnamic acid methyl ester, 4-(3-hydroxypropyloxy)cinnamic acid methyl ester, 4-(2-hydroxyethyloxy)cinnamic acid methyl ester, 4-hydroxymethyloxycinnamic acid methyl ester, cinnamic acid methyl ester, 4-hydroxycinnamic acid methyl ester, 4-(8-hydroxyoctyloxy)cinnamic acid ethyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid ethyl ester, 4-(4-hydroxybutyloxy)cinnamic acid ethyl ester, 4-(3-hydroxypropyloxy)cinnamic acid ethyl ester, 4-(2-hydroxyethyloxy)cinnamic acid ethyl ester, 4-hydroxymethyloxycinnamic acid ethyl ester, 4-hydroxycinnamic acid ethyl ester, 4-(8-hydroxyoctyloxy)cinnamic acid phenyl Ester, 4-(6-hydroxyhexyloxy)cinnamic acid phenyl ester, 4-(4-hydroxybutyloxy)cinnamic acid phenyl ester, 4-(3-hydroxypropyloxy)cinnamic acid phenyl ester, 4-(2-hydroxyethyloxy)cinnamic acid phenyl ester, 4-hydroxymethyloxycinnamic acid phenyl ester, 4-hydroxycinnamic acid phenyl ester, 4-(8-hydroxyoctyloxy)cinnamic acid biphenyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid biphenyl ester, 4-(4-hydroxy butyloxy)cinnamic acid biphenyl ester, 4-(3-hydroxypropyloxy)cinnamic acid biphenyl ester, 4-(2-hydroxyethyloxy)cinnamic acid biphenyl ester, 4-hydroxymethyloxycinnamic acid biphenyl ester, 4-hydroxycinnamic acid biphenyl ester, cinnamic acid 8-hydroxyoctyl ester, cinnamic acid 6-hydroxyhexyl ester, cinnamic acid 4-hydroxybutyl ester, cinnamic acid 3-hydroxypropyl ester, cinnamic acid 2-hydroxyethyl ester, cinnamic acid hydroxymethyl ester,4-(8-hydroxyoctyloxy)azobenzene, 4-(6-hydroxyhexyloxy)azobenzene, 4-(4-hydroxybutyloxy)azobenzene, 4-(3-hydroxypropyloxy)azobenzene, 4-(2-hydroxyethyloxy)azobenzene, 4-hydroxymethyloxyazobenzene, 4-hydroxyazobenzene, 4-(8-hydroxyoctyloxy)chalcone, 4-(6-hydroxyhexyloxy)chalcone, 4-(4-hydroxybutyloxy)chalcone, 4-(3-hydroxypropyloxy)chalcone , 4-(2-hydroxyethyloxy)chalcone, 4-hydroxymethyloxychalcone, 4-hydroxychalcone, 4'-(8-hydroxyoctyloxy)chalcone, 4'-(6-hydroxyhexyloxy)chalcone, 4'-(4-hydroxybutyloxy)chalcone, 4'-(3-hydroxypropyloxy)chalcone, 4'-(2-hydroxyethyloxy)chalcone, 4'-hydroxymethyloxychalcone, 4'-hydroxychalcone, 7-(8-hydroxyoctyloxy)coumarin, 7-(6-hydroxyhexyloxy)coumarin , 7-(4-hydroxybutyloxy)coumarin, 7-(3-hydroxypropyloxy)coumarin, 7-(2-hydroxyethyloxy)coumarin, 7-hydroxymethyloxycoumarin, 7-hydroxycoumarin, 6-(8-hydroxyoctyloxy)coumarin, 6-(6-hydroxyhexyloxy)coumarin, 6-(4-hydroxybutyloxy)coumarin, 6-(3-hydroxypropyloxy)coumarin, 6-(2-hydroxyethyloxy)coumarin, 6-hydroxymethyloxycoumarin, 6-hydroxycoumarin, 4-[4-(8 4-[4-(6-hydroxyoctyloxy)benzoyl]cinnamic acid methyl ester, 4-[4-(6-hydroxyhexyloxy)benzoyl]cinnamic acid methyl ester, 4-[4-(4-hydroxybutyloxy)benzoyl]cinnamic acid methyl ester, 4-[4-(3-hydroxypropyloxy)benzoyl]cinnamic acid methyl ester, 4-[4-(2-hydroxyethyloxy)benzoyl]cinnamic acid methyl ester, 4-[4-hydroxymethyloxybenzoyl]cinnamic acid methyl ester, 4-[4-hydroxybenzoyl]cinnamic acid methyl ester,4-[4-(8-hydroxyoctyloxy)benzoyl]cinnamic acid ethyl ester, 4-[4-(6-hydroxyhexyloxy)benzoyl]cinnamic acid ethyl ester, 4-[4-(4-hydroxybutyloxy)benzoyl]cinnamic acid ethyl ester, 4-[4-(3-hydroxypropyloxy)benzoyl]cinnamic acid ethyl ester, 4-[4-(2-hydroxyethyloxy)benzoyl]cinnamic acid ethyl ester, 4-[4-hydroxymethyloxybenzoyl]cinnamic acid ethyl ester, 4-[4-hydroxybenzoyl]cinnamic acid cinnamic acid ethyl ester, 4-[4-(8-hydroxyoctyloxy)benzoyl]cinnamic acid tert-butyl ester, 4-[4-(6-hydroxyhexyloxy)benzoyl]cinnamic acid tert-butyl ester, 4-[4-(4-hydroxybutyloxy)benzoyl]cinnamic acid tert-butyl ester, 4-[4-(3-hydroxypropyloxy)benzoyl]cinnamic acid tert-butyl ester, 4-[4-(2-hydroxyethyloxy)benzoyl]cinnamic acid tert-butyl ester, 4-[4-hydroxymethyl 4-[4-(4-hydroxypropyloxy)benzoyl]cinnamic acid phenyl ester, 4-[4-(2-hydroxyethyloxy)benzoyl]cinnamic acid phenyl ester, 4-[4-hydroxymethyloxy)benzoyl]cinnamic acid tert-butyl ester, 4-[4-(8-hydroxyoctyloxy)benzoyl]cinnamic acid phenyl ester, 4-[4-(6-hydroxyhexyloxy)benzoyl]cinnamic acid phenyl ester, 4-[4-(4-hydroxybutyloxy)benzoyl]cinnamic acid phenyl ester, 4-[4-(3-hydroxypropyloxy)benzoyl]cinnamic acid phenyl ester, 4-[4-(2-hydroxyethyloxy)benzoyl]cinnamic acid phenyl ester, 4-[4-hydroxymethyloxybenzoyl ]cinnamic acid phenyl ester, 4-[4-hydroxybenzoyl]cinnamic acid phenyl ester, 4-[4-(8-hydroxyoctyloxy)benzoyl]cinnamic acid biphenyl ester, 4-[4-(6-hydroxyhexyloxy)benzoyl]cinnamic acid biphenyl ester, 4-[4-(4-hydroxybutyloxy)benzoyl]cinnamic acid biphenyl ester, 4-[4-(3-hydroxypropyloxy)benzoyl]cinnamic acid biphenyl ester, 4-[4-(2-hydroxyethyloxy)benzoyl]cinnamic acid biphenyl ester,4-[4-hydroxymethyloxybenzoyl]cinnamic acid biphenyl ester, 4-[4-hydroxybenzoyl]cinnamic acid biphenyl ester, 4-benzoylcinnamic acid 8-hydroxyoctyl ester, 4-benzoylcinnamic acid 6-hydroxyhexyl ester, 4-benzoylcinnamic acid 4-hydroxybutyl ester, 4-benzoylcinnamic acid 3-hydroxypropyl ester, 4-benzoylcinnamic acid 2-hydroxyethyl ester, 4-benzoylcinnamic acid hydroxymethyl ester, 4-[4-(8-hydroxyoctyloxy)benzoyl]chalcone, 4-[4-(6-hydroxyhexyloxy)benzoyl]chalcone, 4-[4-(4-hydroxybutyloxy)benzoyl]chalcone, 4-[4-( 4-[4-(3-hydroxypropyloxy)benzoyl]chalcone, 4-[4-(2-hydroxyethyloxy)benzoyl]chalcone, 4-(4-hydroxymethyloxybenzoyl)chalcone, 4-(4-hydroxybenzoyl)chalcone, 4'-[4-(8-hydroxyoctyloxy)benzoyl]chalcone, 4'-[4-(6-hydroxyhexyloxy)benzoyl]chalcone, 4'-[4-(4-hydroxybutyloxy)benzoyl]chalcone, 4'-[4-(3-hydroxypropyloxy)benzoyl]chalcone, 4'-[4-(2-hydroxyethyloxy)benzoyl]chalcone, 4'-(4-hydroxymethyloxybenzoyl)chalcone, 4'-(4-hydroxybenzoyl)chalcone, and the like.

[0036] Specific examples of the low molecular weight compound having a photoalignable group and a carboxy group, which is component (A), include cinnamic acid, ferulic acid, 4-methoxycinnamic acid, 4-propoxycinnamic acid, 3,4-dimethoxycinnamic acid, coumarin-3-carboxylic acid, and 4-(N,N-dimethylamino)cinnamic acid.

[0037] Specific examples of the component (A), a low molecular weight compound having a photoalignable group and an amide group, include cinnamic acid amide, 4-methylcinnamic acid amide, 4-ethylcinnamic acid amide, 4-methoxycinnamic acid amide, and 4-ethoxycinnamic acid amide.

[0038] Specific examples of the component (A), a low molecular weight compound having a photoalignable group and an amino group, include 4-aminocinnamic acid methyl ester, 4-aminocinnamic acid ethyl ester, 3-aminocinnamic acid methyl ester, and 3-aminocinnamic acid ethyl ester.

[0039] Specific examples of the low molecular weight compound having a photoalignable group and an alkoxysilyl group, which is the component (A), include 4-(3-trimethoxysilylpropyloxy)cinnamic acid methyl ester, 4-(3-triethoxysilylpropyloxy)cinnamic acid methyl ester, 4-(3-trimethoxysilylpropyloxy)cinnamic acid ethyl ester, 4-(3-triethoxysilylpropyloxy)cinnamic acid ethyl ester, 4-(3-trimethoxysilylhexyloxy)cinnamic acid methyl ester, 4-(3-triethoxysilylhexyloxy)cinnamic acid methyl ester, 4-(3-trimethoxysilylhexyloxy)cinnamic acid ethyl ester, and 4-(3-triethoxysilylhexyloxy)cinnamic acid ethyl ester.

[0040] As the low molecular weight compound of the component (A), a compound in which a polymerizable group is bonded via a spacer to a group in which a photoalignable moiety and a thermally reactive moiety are bonded, as represented by the following formula (a-1): (In the formula, R １０１ represents a hydroxy group, an amino group, a hydroxyphenoxy group, a carboxyphenoxy group, an aminophenoxy group, an aminocarbonylphenoxy group, a phenylamino group, a hydroxyphenylamino group, a carboxyphenylamino group, an aminophenylamino group, a hydroxyalkylamino group, or a bis(hydroxyalkyl)amino group; X １０１ represents a phenylene group which may be substituted with any substituent, and the hydrogen atoms on the benzene ring in the definitions of these substituents may be substituted with a substituent.

[0041] In the case where a hydrogen atom on the benzene ring may be substituted with a substituent, examples of the substituent include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group; haloalkyl groups such as a trifluoromethyl group; alkoxy groups such as a methoxy group and an ethoxy group; halogen atoms such as an iodine atom, a bromine atom, a chlorine atom, and a fluorine atom; a cyano group; and a nitro group.

[0042] The above R １０１ Among these, a hydroxy group and an amino group are preferred, and a hydroxy group is particularly preferred.

[0043] The spacer is a divalent group selected from a linear alkylene group, a branched alkylene group, a cyclic alkylene group, and a phenylene group, or a group formed by bonding multiple divalent groups. In this case, examples of the bond between the divalent groups constituting the spacer, the bond between the spacer and the group represented by formula (a-1), and the bond between the spacer and the polymerizable group include a single bond, an ester bond, an amide bond, a urea bond, and an ether bond. When there are multiple divalent groups, the divalent groups may be the same or different, and when there are multiple bonds, the bonds may be the same or different.

[0044] Specific examples of such a low molecular weight compound in which a polymerizable group is bonded to a group in which a photoalignment moiety and a thermally reactive moiety are bonded, which is component (A), include 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid, 4-(6-acryloxyhexyl-1-oxy)cinnamic acid, 4-(3-methacryloxypropyl-1-oxy)cinnamic acid, 4-(4-(3-methacryloxypropyl-1-oxy)acryloxy)benzoic acid, 4-(4-(6-methacryloxyhexyl-1-oxy)benzoyloxy)cinnamic acid, 4-(6-methacryloxyhexyl-1-oxy)cinnamamide, 4-(6-methacryloxyhexyl-1-oxy)-N-(4-cyanophenyl)cinnamamide, and 4-(6-methacryloxyhexyl-1-oxy)-N-bishydroxyethylcinnamamide.

[0045] The low molecular weight photo-alignment component (A) can be exemplified by the above specific examples, but is not limited to these.

[0046] As described above, in the present invention, a low molecular weight compound can be used as component (A). Component (A) may also be a mixture of one or more low molecular weight compounds.

[0047] <Polymer Having Photoalignment Group and Thermally Crosslinkable Group> In the cured film-forming composition of the present invention, the polymer of component (A) is a polymer having a photoalignment group, i.e., a polymer having a functional group of a structural moiety that is photodimerizable or photoisomerizable as the photoalignment group, and is particularly preferably an acrylic copolymer having at least a photodimerization moiety. Furthermore, it is desirable that the polymer be an acrylic copolymer having, in addition to the photodimerization moiety, one group selected from the group consisting of a hydroxy group, a carboxy group, an amide group, an amino group, and an alkoxysilyl group (hereinafter, these groups are also referred to as the thermally crosslinkable moiety).

[0048] In the present invention, the acrylic copolymer refers to a copolymer obtained by polymerizing a monomer having an unsaturated double bond, such as an acrylic acid ester, a methacrylic acid ester, or styrene.

[0049] The acrylic copolymer (hereinafter also referred to as the specific copolymer) having a photodimerization moiety and a thermal crosslinking moiety of the component (A) may be any acrylic copolymer having such a structure, and there are no particular limitations on the types of the main chain skeleton and side chains of the polymer constituting the acrylic copolymer.

[0050] Examples of the photodimerization moiety include a cinnamoyl group, a chalcone group, a coumarin group, and an anthracene group. Among these, a cinnamoyl group is preferred because of its high transparency in the visible light region and high photodimerization reactivity. More preferred cinnamoyl groups and substituents containing a cinnamoyl structure include structures represented by the following formula [1] or formula [2]. In this specification, a cinnamoyl group in which the benzene ring is a naphthalene ring is also included in the "cinnamoyl group" and "substituent containing a cinnamoyl structure."

[0051] In the above formula [1], X １represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a biphenyl group, in which case the hydrogen atoms on the phenyl group and the biphenyl group may be substituted with either a halogen atom or a cyano group.

[0052] In the above formula [2], X ２ represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. In this case, a plurality of alkyl groups having 1 to 18 carbon atoms, phenyl groups, biphenyl groups, and cyclohexyl groups may be bonded via one or more bonds selected from a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, a carbonyl bond, or a combination thereof.

[0053] In the above formulas [1] and [2], A represents any one of formulas [A1], [A2], [A3], [A4], [A5] and [A6].

[0054] In the above formula [A1], formula [A2], formula [A3], formula [A4], formula [A5] and formula [A6], R ３１ , R ３２ , R ３３ , R ３４ , R ３５ , R ３６ , R ３７ and R ３８ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group, or a cyano group.

[0055] The thermal crosslinking moiety is a moiety that bonds with the crosslinking agent (B) by heating, and specific examples thereof include a hydroxy group, a carboxy group, an amide group, an amino group, and an alkoxysilyl group.

[0056] The acrylic copolymer of component (A) preferably has a weight-average molecular weight of 3,000 to 200,000. If the weight-average molecular weight is too high, exceeding 200,000, the solubility in solvents may decrease, leading to poor handling, whereas if the weight-average molecular weight is too low, less than 3,000, the copolymer may not cure sufficiently during heat curing, resulting in poor solvent resistance and poor heat resistance.

[0057] The acrylic copolymer having a photodimerization moiety and a thermal crosslinking moiety, component (A), can be synthesized simply by copolymerizing a monomer having a photodimerization moiety with a monomer having a thermal crosslinking moiety.

[0058] Examples of the monomer having a photodimerization moiety include monomers having a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, etc. Among these, monomers having a cinnamoyl group are particularly preferred because of their high transparency in the visible light region and high photodimerization reactivity.

[0059] Among these, monomers having a cinnamoyl group or a substituent containing a cinnamoyl structure represented by the above formula [1] or formula [2] are more preferred. Specific examples of such monomers include monomers represented by the following formula [3] or formula [4]:

[0060] In the above formula [3], X １ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a biphenyl group. In this case, the hydrogen atoms on the phenyl group and the biphenyl group may be substituted with either a halogen atom or a cyano group. １ and L ２ each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond.

[0061] In the above formula [4], X ２ represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. In this case, a plurality of alkyl groups having 1 to 18 carbon atoms, phenyl groups, biphenyl groups, and cyclohexyl groups may be bonded via one or more bonds selected from a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, a carbonyl bond, or a combination thereof.

[0062] In the above formula [3] and formula [4], X ３ and X ５each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring, or a divalent aliphatic ring. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear.

[0063] In the above formula [3] and formula [4], X ４ represents a polymerizable group. Specific examples of the polymerizable group include an acryloyl group, a methacryloyl group, a styrene group, a maleimide group, an acrylamide group, and a methacrylamide group.

[0064] In the above formulas [3] and [4], A represents any one of formulas [A1], [A2], [A3], [A4], [A5] and [A6] as described above.

[0065] Examples of the monomer having a thermal crosslinking moiety include 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; acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl ester), methyl acrylate, ... monomers having a phenolic hydroxy group such as hydroxystyrene, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)maleimide, N-(hydroxyphenyl)maleimide; monomers having an amide group such as acrylamide and methacrylamide; monomers having an alkoxysilyl group such as methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, acryloyloxypropyltrimethoxysilane and acryloyloxypropyltriethoxysilane; and monomers having an amino group such as dimethylaminoethyl methacrylate, diethylamino methacrylate and tert-butylaminoethyl methacrylate.

[0066] The amounts of the monomer having a photodimerization moiety and the monomer having a thermal crosslinking moiety used to obtain the specific copolymer are preferably 40% by mass to 95% by mass, and 5% by mass to 60% by mass, based on the total amount of all monomers used to obtain the specific copolymer. By setting the content of the monomer having a photodimerization moiety to 40% by mass or more, high sensitivity and good liquid crystal alignment properties can be imparted. On the other hand, by setting the content to 95% by mass or less, sufficient thermosetting properties can be imparted, and high sensitivity and good liquid crystal alignment properties can be maintained.

[0067] In addition, in the cured film-forming composition of the present invention, when obtaining the specific copolymer, a monomer having a photodimerization moiety and a thermal crosslinking moiety (hereinafter, these may also be referred to as specific functional groups) and a monomer copolymerizable therewith (hereinafter, also referred to as a monomer having a non-reactive functional group) may be used in combination.

[0068] Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, etc. Specific examples of the above-mentioned monomers are listed below, but the present invention is not limited to these.

[0069] Examples of the acrylic acid ester compounds include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, glycidyl 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.

[0070] Examples of the methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl 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, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

[0071] Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0072] Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

[0073] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0074] The method for obtaining the specific copolymer used in the cured film-forming composition of the present invention is not particularly limited, and examples thereof include a method of polymerizing a monomer having a specific functional group (a monomer having a photodimerization moiety and a monomer having a thermal crosslinking moiety), optionally a monomer having a non-reactive functional group, a polymerization initiator, and the like in a solvent in which these monomers coexist at a temperature of 50°C to 110°C. The solvent used in this case is not particularly limited as long as it dissolves the monomer having the specific functional group, the optional monomer having a non-reactive functional group, the polymerization initiator, and the like. Specific examples include the solvents described below in the section on solvents.

[0075] The specific copolymer thus obtained is usually in the form of a solution dissolved in a solvent, and can be used as is as the polymer solution of component (A) in the present invention.

[0076] In addition, the solution of the specific copolymer obtained as described above can be reprecipitated by adding diethyl ether, water, or the like under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal pressure or reduced pressure to obtain a powder of the specific copolymer.By such an operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a powder of the purified specific copolymer can be obtained.If the specific copolymer cannot be sufficiently purified by one operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated.

[0077] In the cured film-forming composition of the present invention, the powder of the specific copolymer may be used as it is as the polymer of component (A), or the powder may be redissolved in, for example, a solvent described below and used in the form of a solution.

[0078] Furthermore, as the polymer of component (A), a polymer obtained by reacting a polymer having an epoxy group in the side chain with a cinnamic acid derivative can also be used.

[0079] The polymer having an epoxy group in the side chain can be, for example, a polymer of a polymerizable unsaturated compound having an epoxy group or a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound.

[0080] Specific examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl 6,7-epoxyheptyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

[0081] Examples of other polymerizable unsaturated compounds include (meth)acrylic acid alkyl esters, (meth)acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other polymerizable unsaturated compounds.

[0082] Specific examples of these include alkyl methacrylates such as hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside, 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, and n-stearyl methacrylate; alkyl acrylates such as methyl acrylate and isopropyl acrylate; and cyclic alkyl methacrylates such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0]methacrylate. ２，６ ] decan-8-yl methacrylate, tricyclo[5.2.1.0 ２，６ ] decan-8-yloxyethyl methacrylate, isobornyl methacrylate, cholestanyl methacrylate, etc.; acrylic acid cyclic alkyl esters such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ２，６ ] decan-8-yl acrylate, tricyclo[5.2.1.0 ２，６ ] decan-8-yloxyethyl acrylate, isobornyl acrylate, cholestanyl acrylate, etc.; methacrylic acid aryl esters such as phenyl methacrylate, benzyl methacrylate, etc.; acrylic acid aryl esters such as phenyl acrylate, benzyl acrylate, etc.; unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate, etc.;

[0083] Examples of bicyclo unsaturated compounds include bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5 , 6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, etc.; maleimide compounds, such as N-phenylmaleimide, N- Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N-(9-acridinyl)maleimide, and the like; unsaturated aromatic compounds, such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like; conjugated diene compounds, such as 1,3-butadiene, Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid; examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; examples of unsaturated dicarboxylic acid anhydrides include the anhydrides of the above-mentioned unsaturated dicarboxylic acids; and examples of polymerizable unsaturated compounds other than those mentioned above include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

[0084] The copolymerization ratio of the polymerizable unsaturated compound having an epoxy group in the polymer having an epoxy group in the side chain is preferably 30% by mass or more, more preferably 50% by mass or more.

[0085] The synthesis of a polymer having an epoxy group in the side chain can be carried out by a known radical polymerization method, preferably in a solvent in the presence of a suitable polymerization initiator.

[0086] Commercially available products may be used as the polymer having an epoxy group in the side chain. Examples of such commercially available products include EHPE3150 and EHPE3150CE (manufactured by Daicel Corporation), UG-4010, UG-4035, UG-4040, and UG-4070 (ARUFON series manufactured by Toagosei Co., Ltd.), ECN-1299 (manufactured by Asahi Kasei Corporation), DEN431 and DEN438 (manufactured by The Dow Chemical Company), and jE Examples of suitable inks include R-152 (manufactured by Mitsubishi Chemical Corporation), Epicron N-660, N-665, N-670, N-673, N-695, N-740, N-770, and N-775 (all manufactured by DIC Corporation (formerly Dainippon Ink and Chemicals, Inc.)), and EOCN-1020, EOCN-102S, and EOCN-104S (all manufactured by Nippon Kayaku Co., Ltd.).

[0087] Examples of the cinnamic acid derivative include cinnamic acid derivatives having a carboxy group, such as those represented by the following formulas (1-1) to (1-5): (In the formula, R １ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, etc.)

[0088] Further, as the cinnamic acid derivative having a carboxy group, in the monomer represented by the above formula [3], X １ Compounds in which is a hydrogen atom are also preferably used.

[0089] The compounds represented by the above formulas (1-1) to (1-5) can be synthesized by appropriately combining standard methods in organic chemistry.

[0090] The reaction product of the polymer having an epoxy group in the side chain and a cinnamic acid derivative can be synthesized by reacting the polymer having an epoxy group as described above with a cinnamic acid derivative, preferably in the presence of a catalyst, preferably in a suitable organic solvent.

[0091] The proportion of the cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 mol, more preferably 0.05 to 1.3 mol, and even more preferably 0.1 to 1.1 mol, per 1 mol of epoxy groups contained in the polymer having epoxy groups.

[0092] The catalyst that can be used here may be an organic base or a compound known as a curing accelerator that accelerates the reaction between an epoxy compound and an acid anhydride.

[0093] Examples of the organic base include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and diazabicycloundecene; and quaternary organic amines such as tetramethylammonium hydroxide. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, pyridine, and 4-dimethylaminopyridine; and quaternary organic amines such as tetramethylammonium hydroxide are preferred.

[0094] Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, and triethanolamine; 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 1,2-dimethylimidazole; dazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyanoethyl)-2-n-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2-phenyl-4 ,5-di[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazolium trimellitate, 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2,4-diamino-6-(2'-n-undecylimidazolyl)ethyl-s imidazole compounds such as 2-methylimidazole, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-triazine, an isocyanuric acid adduct of 2-methylimidazole, an isocyanuric acid adduct of 2-phenylimidazole, and an isocyanuric acid adduct of 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine; organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenyl phosphite;

[0095] quaternary phosphonium salts such as benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o,o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, and tetraphenylphosphonium tetraphenylborate; diazabicycloalkene compounds such as 1,8-diazabicyclo[5.4.0]undecene-7 and organic acid salts thereof; quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride; boron compounds such as boron trifluoride and triphenyl borate; metal halide compounds such as zinc chloride and stannic chloride; high-melting point dispersion-type latent curing accelerators such as amine addition-type accelerators such as dicyandiamide and adducts of amines and epoxy resins; microcapsule-type latent curing accelerators in which the surface of the curing accelerators such as the imidazole compounds, organic phosphorus compounds, and quaternary phosphonium salts is coated with a polymer; amine salt-type latent curing accelerators; and latent curing accelerators such as high-temperature dissociation-type thermal cationic polymerization-type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

[0096] Of these, preferred are quaternary phosphonium salts such as benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o,o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, and tetraphenylphosphonium tetraphenylborate; and quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

[0097] The catalyst is preferably used in an amount of 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, and even more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymer having an epoxy group.

[0098] Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, and alcohol compounds. Of these, ether compounds, ester compounds, ketone compounds, and alcohol compounds are preferred from the viewpoints of solubility of the raw materials and the product and ease of product purification. The solvent is used in an amount such that the solids concentration (the proportion of the mass of components other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1 mass % or more, more preferably 5 to 50 mass %.

[0099] The reaction temperature is preferably 0 to 200° C., more preferably 50 to 150° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

[0100] In this way, a solution containing a reaction product of the polymer having an epoxy group and the cinnamic acid derivative is obtained. This solution may be used as it is for the preparation of a cured film-forming composition, or the polymer contained in the solution may be isolated and then used for the preparation of a cured film-forming composition, or the isolated polymer may be purified and then used for the preparation of a cured film-forming composition.

[0101] In this embodiment, the acrylic copolymer of component (A) may be a mixture of multiple specific copolymers.

[0102] As described above, in the present invention, a high molecular weight specific copolymer can be used as component (A), and component (A) may also be a mixture of one or more specific copolymers.

[0103] [Component (B)] The component (B) contained in the cured film-forming composition of the present invention is a polymer having a structural unit having an N-hydroxymethyl group or an N-alkoxymethyl group, and more specifically, a polymer obtained by polymerizing a monomer having an N-alkoxymethyl group or an N-hydroxymethyl group (hereinafter, also referred to as specific polymer 2).

[0104] Preferred examples of the monomer having an N-alkoxymethyl group or an N-hydroxymethyl group include compounds represented by the following formula (X1): (In the formula, R ３１ represents a hydrogen atom or a methyl group, R ３２ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms)

[0105] Specific examples of the compound represented by formula (X1) include 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, where (meth)acrylamide refers to both methacrylamide and acrylamide.

[0106] The specific polymer 2, which is the component (B), may be a copolymer obtained by copolymerizing a monomer having a group represented by the above formula (1) in addition to a monomer having an N-alkoxymethyl group or an N-hydroxymethyl group.

[0107] In the above formula (1), Q １ The alkyl group having 1 to 6 carbon atoms represented by is preferably an alkyl group having 1 to 5 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 4-methyl-n-pentyl group, a 5-methyl-n-pentyl group, a 6-methyl-n-pentyl group, a 7-methyl-n-pentyl group, a 8-methyl-n-pentyl group, a 9-methyl-n-pentyl group, a 10-methyl-n-pentyl group, a 11-methyl-n-pentyl group, a 12-methyl-n-pentyl group, a 13-methyl-n-pentyl group, a 14-methyl-n-pentyl group, a 15-methyl-n-pentyl group, a 16-methyl-n-pentyl group, a 17-methyl-n-pentyl group, a 18-methyl-n-pentyl group, a 19-methyl-n-pentyl group, a 20-methyl-n-pentyl group, a 21-methyl-n-pentyl group, a 22-methyl-n-pentyl group, a 23-methyl-n-pentyl group, a 24-methyl-n-pentyl group, a 25-methyl-n-pentyl group, a 26-methyl-n-pentyl group, a Examples of such alkyl groups include butyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Among these, methyl, ethyl, n-propyl, n-butyl, and isobutyl groups are preferred.

[0108] In the above formula (1), Q １ The alkoxy group having 1 to 6 carbon atoms represented by is preferably an alkoxy group having 1 to 5 carbon atoms.

[0109] Examples of such alkoxy groups include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 5-methyl-n-pentyloxy group, a 6-methyl-n-pentyloxy group, a 7-methyl-n-pentyloxy group, a 8-methyl-n-pentyloxy group, a 9-methyl-n-pentyloxy group, a 10-methyl-n-pentyloxy group, a 11-methyl-n-butoxy group, a 22-methyl-n-butoxy group, a 23-methyl-n-pentyloxy group, a 24-methyl-n-pentyloxy group, a 25-methyl-n-pentyloxy group, a 26-methyl-n-pentyloxy group, a 27-methyl-n-pentyloxy group, a 28-methyl-n-pentyloxy group, a 29-methyl-n-pentyloxy group, a 30-methyl-n-pentyloxy group, a 31-methyl-n-pentyloxy group, a 32-methyl-n-pentyloxy group, a 33-methyl-n-pentyloxy group, a 34-methyl-n-pentyloxy group, a 35-methyl-n-pentyloxy group, a 36 Examples thereof include an ethyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, a 1-ethyl-2-methyl-n-propoxy group, a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

[0110] Among these, a methoxy group, an ethoxy group, an n-propoxy group, and the like are preferred.

[0111] In the above formula (1), Q ２ is O, S or NQ ３ represents Q ３ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ３ The alkyl group having 1 to 4 carbon atoms represented by Q １ Among the specific examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I), those having 1 to 4 carbon atoms are preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred, with a methyl group being more preferred.

[0112] Examples of the monomer having a group represented by formula (1) include acetoacetoxyethyl acrylate and acetoacetoxyethyl methacrylate.

[0113] The amount of the monomer having an N-hydroxymethyl group or an N-alkoxymethyl group used to obtain a polymer having a structural unit having an N-hydroxymethyl group or an N-alkoxymethyl group is preferably 10 mol % to 100 mol %, more preferably 30 mol % to 100 mol %, and even more preferably 50 mol % to 100 mol %, based on the total amount of all monomers used to obtain Specific Polymer 2.

[0114] When the component (B) is a polymer having a structural unit having an N-hydroxymethyl group or an N-alkoxymethyl group and a structural unit having a partial structure represented by formula (1), the amounts of the monomer having an N-hydroxymethyl group or an N-alkoxymethyl group and the monomer having a group represented by formula (1) used to obtain the polymer are, based on the total amount of all monomers used to obtain specific polymer 2, preferably 10 mol % to 99.9 mol %, more preferably 30 mol % to 99 mol %, and even more preferably 50 mol % to 95 mol %, and the amount of the monomer having a group represented by formula (1) is preferably 0.1 mol % to 90 mol %, more preferably 1 mol % to 70 mol %, and even more preferably 5 mol % to 50 mol %.

[0115] When obtaining a polymer having a structural unit having an N-hydroxymethyl group or an N-alkoxymethyl group and, if desired, a structural unit represented by the above formula (1), a monomer having a non-reactive functional group, as exemplified in the section on component (A), can be used. When the total amount of the monomer having an N-hydroxymethyl group or an N-alkoxymethyl group and the monomer having the group represented by formula (1) is less than 100 mol%, the amount of the monomer having a non-reactive functional group used is the remaining portion.

[0116] The weight average molecular weight of the polymer that is component (B) is preferably from 1,000 to 500,000, more preferably from 2,000 to 200,000, even more preferably from 3,000 to 150,000, and particularly preferably from 3,000 to 50,000.

[0117] These polymers of component (B) can be used alone or in combination of two or more.

[0118] In the cured film-forming composition of the present invention, the content of the polymer having a structural unit having an N-hydroxymethyl group or an N-alkoxymethyl group as component (B) and, if desired, a structural unit having a partial structure represented by formula (1) above is preferably 1 to 2,000 parts by mass, and more preferably 5 to 1,000 parts by mass, based on 100 parts by mass of the compound as component (A).

[0119] [Component (C)] The cured film-forming composition of the present invention contains, as component (C), a cyclodextrin derivative in which some or all of the hydroxy groups have been modified.

[0120] Examples of the cyclodextrin derivative in which some or all of the hydroxy groups have been modified as component (C) include methylated cyclodextrins such as methyl-α-cyclodextrin, methyl-β-cyclodextrin, and methyl-γ-cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl-γ ... and hydroxyalkyl cyclodextrins such as 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3-dihydroxypropyl-β-cyclodextrin, and 2,3-dihydroxypropyl-γ-cyclodextrin.

[0121] In the cured film-forming composition of the present invention, the compound of component (C) may be used in the form of a powder, or in the form of a solution obtained by redissolving a purified powder in a solvent described below.

[0122] In the cured film-forming composition of the present invention, the compound of component (C) may be a mixture of two or more compounds included in the definition of component (C).

[0123] The content of the compound of component (C) in the cured film-forming composition of the present invention is preferably 10 parts by mass to 1,000 parts by mass, and more preferably 30 parts by mass to 500 parts by mass, based on 100 parts by mass of the photoalignment component of component (A).

[0124] [Component (D)] The cured film-forming composition of the present invention may further contain a crosslinking catalyst as component (D) in addition to the above-described components (A), (B), and (C). Examples of the crosslinking catalyst as component (D) include acids and thermal acid generators. This component (D) is effective in accelerating the thermal curing reaction in the formation of a cured film using the cured film-forming composition of the present invention.

[0125] When an acid or thermal acid generator is used as component (D), component (D) is not particularly limited as long as it is a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof, or a compound that thermally decomposes during pre-bake or post-bake to generate an acid, i.e., a compound that thermally decomposes at a temperature of 60°C to 250°C to generate an acid.

[0126] Examples of such compounds include sulfonic acids such as hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, 1,2-ethanedisulfonic acid, and methanesulfonic anhydride, as well as hydrates and salts thereof.

[0127] Examples of the compound that generates an acid when heated include bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylene tris(methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-4-toluenesulfonamide, and the compounds represented by the following formulae [TAG-1] to [TAG-41].

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135] The component (D) is commercially available, and examples thereof include TA-100, TA-100FG, IK-1, and IK-1FG (all manufactured by San-Apro Ltd.), San-Aid (registered trademark) SI-B2A, San-Aid (registered trademark) SI-B7, San-Aid (registered trademark) SI-B3A, San-Aid (registered trademark) SI-B3, San-Aid (registered trademark) SI-B5, San-Aid (registered trademark) SI-B4, San-Aid (registered trademark) SI-150, San-Aid (registered trademark) SI-110, San-Aid (registered trademark) SI-60, San-Aid (registered trademark) SI-80, and San-Aid (registered trademark) SI-100 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

[0136] The content of component (D) in the cured film-forming composition of the present invention is 0.01 to 20 parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and even more preferably 0.1 to 6 parts by mass, per 100 parts by mass of the photoalignment component (A). By ensuring that the content of component (D) is 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted, and high sensitivity to light exposure can also be imparted. Furthermore, by ensuring that the content is 20 parts by mass or less, the storage stability of the cured film-forming composition can be improved.

[0137] [Component (E)] The cured film-forming composition of the present invention may also contain, as component (E), a component that improves the adhesiveness of the cured film to be formed (hereinafter also referred to as an adhesion-improving component).

[0138] The adhesion improving component (E) can link the polymerizable functional group of the polymerizable liquid crystal with the cross-linking reaction site of the alignment material by a covalent bond so as to improve the adhesion between the alignment material obtained from the cured film-forming composition of the present invention and the polymerizable liquid crystal layer. As a result, the retardation material of the present embodiment obtained by laminating the cured polymerizable liquid crystal on the alignment material of the present embodiment can maintain strong adhesion even under high temperature and high temperature conditions and can exhibit high durability against peeling, etc.

[0139] The component (E) is preferably a monomer or polymer having a group selected from a hydroxy group and an N-alkoxymethyl group, and a polymerizable group. Examples of such component (E) include a compound having a hydroxy group and a (meth)acrylic group, a compound having an N-alkoxymethyl group and a (meth)acrylic group, and a polymer having an N-alkoxymethyl group and a (meth)acrylic group. Specific examples of each are shown below.

[0140] An example of component (E) is a polyfunctional acrylate containing a hydroxy group (hereinafter also referred to as a hydroxy group-containing polyfunctional acrylate). Examples of the hydroxy group-containing polyfunctional acrylate that is component (E) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

[0141] An example of component (E) is a compound having one acrylic group and one or more hydroxy groups.

[0142] Specific examples of compounds having one acrylic group and one or more hydroxy groups include the following compounds: (In the above formula, R １１ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10.

[0143] Furthermore, examples of the compound of component (E) include compounds having at least one polymerizable group containing a C═C double bond and at least one N-alkoxymethyl group in one molecule.

[0144] Examples of the polymerizable group containing a C═C double bond include an acrylic group, a methacrylic group, a vinyl group, an allyl group, and a maleimide group.

[0145] As a preferred example of the compound having at least one polymerizable group containing a C═C double bond and at least one N-alkoxymethyl group in one molecule, there can be mentioned a compound represented by the following formula (X1): (In formula (X1), R ３１ represents a hydrogen atom or a methyl group, R ３２represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms)

[0146] Specific examples of the compound represented by formula (X1) include 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, where (meth)acrylamide refers to both methacrylamide and acrylamide.

[0147] Preferred examples of the compound having a polymerizable group containing a C═C double bond and an N-alkoxymethyl group as component (E) include the following compounds.

[0148] The content of the component (E) in the liquid crystal aligning agent cured film-forming composition according to the embodiment of the present invention is preferably 1 part by mass to 300 parts by mass, and more preferably 5 parts by mass to 200 parts by mass, relative to 100 parts by mass of the alignment component (A).

[0149] [Other Additives] The cured film-forming composition of the present invention may contain other additives as long as the effects of the present invention are not impaired. Examples of other additives include a sensitizer. The sensitizer is effective in accelerating the photoreaction when forming a cured film on the surface of the optical film of the present invention.

[0150] Examples of the sensitizer include derivatives of benzophenone, anthracene, anthraquinone, thioxanthone, etc., and nitrophenyl compounds, etc. Among these, N,N-diethylaminobenzophenone, which is a benzophenone derivative, and 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4-nitrostilbene, 4-nitrobenzophenone, and 5-nitroindole, which are nitrophenyl compounds, are particularly preferred.

[0151] These sensitizers are not particularly limited to those mentioned above, and these can be used alone or in combination of two or more compounds.

[0152] In an embodiment of the present invention, the proportion of the sensitizer used is preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass, per 100 parts by mass of component (A). If this proportion is too small, the effect as a sensitizer may not be fully obtained, whereas if it is too large, the transmittance of the formed cured film may decrease or the coating film may become rough.

[0153] The cured film-forming composition of the present invention may also contain other additives such as a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, and an antioxidant, as long as the effects of the present invention are not impaired.

[0154] [Solvent] The cured film-forming composition of the present invention is often used in the form of a solution dissolved in a solvent. The solvent used in this case is one that dissolves components (A), (B), and (C), and optionally components (D) and (E), and other additives, and the type and structure of the solvent are not particularly limited as long as it has such dissolving ability.

[0155] Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, cyclopentyl methyl ether, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, and 3-methyl-2-pentanone. , 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, n-propyl acetate, isopropyl acetate, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

[0156] The solvent is commercially available, and examples thereof include Neoethanol (registered trademark) PM, Neoethanol (registered trademark) MIP, Neoethanol (registered trademark) IPM, Neoethanol (registered trademark) IPE, Neoethanol (registered trademark) PHI, Neoethanol (registered trademark) MHI, Neoethanol (registered trademark) PIP, Neoethanol (registered trademark) HIMTE, Neoethanol (registered trademark) PHM, Neoethanol (registered trademark) IPME, and Neoethanol (registered trademark) P-7 (all manufactured by Taishin Chemical Co., Ltd.).

[0157] These solvents can be used alone or in combination of two or more. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, cyclohexanone, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and Neoethanol (registered trademark) IPM are more preferred because of their excellent film-forming properties and high safety.

[0158] <Preparation of Cured Film-Forming Composition> As described above, the cured film-forming composition of the present invention comprises a photoalignment component (A), a polymer (B) having a structural unit having an N-hydroxymethyl group or an N-alkoxymethyl group and, optionally, a structural unit having a partial structure represented by formula (1), a cyclodextrin derivative (C) in which some or all of the hydroxy groups have been modified, and, optionally, a crosslinking catalyst (D) dissolved in a solvent. Furthermore, the composition may optionally contain an adhesion-improving component (E). Other additives may also be added as long as they do not impair the effects of the present invention.

[0159] Preferred examples of the cured film-forming composition of the present invention are as follows: [1]: A cured film-forming composition containing (A) a photo-alignment component, 1 part by mass to 2,000 parts by mass of (B) component based on 100 parts by mass of the component (A), and 10 parts by mass to 1,000 parts by mass of (C) component based on 100 parts by mass of the photo-alignment component (A).

[0160] [2]: A cured film-forming composition comprising: (A) a photo-alignment component; 1 part by mass to 2,000 parts by mass of a (B) component based on 100 parts by mass of the (A) component; 10 parts by mass to 1,000 parts by mass of a (C) component based on 100 parts by mass of the (A) photo-alignment component; and (D) a crosslinking catalyst in an amount of 0.01 parts by mass to 20 parts by mass per 100 parts by mass of the (A) component.

[0161] [3]: A cured film-forming composition comprising: (A) a photo-alignment component; 1 part by mass to 2,000 parts by mass of a (B) component based on 100 parts by mass of the (A) component; 10 parts by mass to 1,000 parts by mass of a (C) component based on 100 parts by mass of the (A) photo-alignment component; 0.01 parts by mass to 20 parts by mass of a (D) crosslinking catalyst relative to 100 parts by mass of the (A) component; and 1 part by mass to 300 parts by mass of a (E) component based on 100 parts by mass of the (A) component.

[0162] The blending ratios, preparation methods, etc., when the cured film-forming composition of the present invention is used as a solution are described in detail below. The solid content of the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1 to 80% by mass, preferably 2 to 60% by mass, and more preferably 3 to 40% by mass. Here, the solid content refers to all components of the cured film-forming composition excluding the solvent.

[0163] The method for preparing the cured film-forming composition of the present invention is not particularly limited. Examples of the preparation method include a method in which the components (A), (C), and optionally the component (D), and further optionally the component (E) are mixed in predetermined proportions with a solution of the component (B) dissolved in a solvent to prepare a homogeneous solution, or a method in which other additives are further added and mixed as necessary at an appropriate stage of this preparation method.

[0164] In preparing the cured film-forming composition of the present invention, as described above, a solution of specific polymer 2 (component (B)) obtained by polymerization in a solvent can be used as is. In this case, for example, component (A), component (C), and, if desired, component (D) and component (E), etc. are added to a solution of component (B) obtained by copolymerizing the aforementioned monomer having an N-hydroxymethyl group or an N-alkoxymethyl group, a monomer having a group represented by formula (1), and, if desired, other monomers, to prepare a homogeneous solution. At this time, additional solvent may be added for the purpose of adjusting the concentration. In this case, the solvent used in the production process of component (B) and the solvent used to adjust the concentration of the cured film-forming composition may be the same or different.

[0165] The prepared solution of the cured film-forming composition is preferably filtered using a filter having a pore size of about 0.2 μm before use in forming the cured film.

[0166] <Cured Film, Alignment Material, and Retardation Material> The cured film-forming composition of the present embodiment can be obtained by applying a solution of the cured film-forming composition to a substrate (e.g., a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate) or a film (e.g., a resin film such as a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, or an acrylic film) by bar coating, spin coating, flow coating, roll coating, slit coating, spin coating followed by slitting, inkjet coating, printing, or the like to form a coating film, and then heating and drying the coating on a hot plate, in an oven, or the like to form a cured film.

[0167] The heating and drying conditions are such that when a cured film is used as a liquid crystal alignment film, the curing reaction proceeds to such an extent that the components of the liquid crystal alignment film are not eluted into the polymerizable liquid crystal solution to be applied thereon, and for example, a heating temperature and a heating time appropriately selected from the ranges of 50°C to 200°C and 0.4 to 60 minutes are used. The heating temperature and heating time are preferably 60°C to 160°C and 0.5 to 10 minutes.

[0168] The thickness of the cured film obtained using the cured film-forming composition of the present invention is, for example, 0.05 μm to 5 μm, and can be appropriately selected taking into consideration the step height and optical and electrical properties of the resin film used as the substrate.

[0169] The cured film obtained using the cured film-forming composition of the present invention thus prepared can be irradiated with polarized UV light to cause the cured film formed on the substrate to function as a liquid crystal alignment film, i.e., a component that aligns compounds having liquid crystal properties, including polymerizable liquid crystals, and can be used as an alignment material.

[0170] The polarized UV irradiation method generally uses ultraviolet to visible light with a wavelength of 150 nm to 450 nm, and is carried out by irradiating linearly polarized light from a vertical or oblique direction at room temperature or in a heated state.

[0171] In the alignment material of the present invention, the cured film that becomes the liquid crystal alignment film has solvent resistance and heat resistance, so that a retardation material made of a polymerizable liquid crystal solution is applied onto this alignment material, and then heated to the phase transition temperature of the liquid crystal to turn the retardation material into a liquid crystal state and align it on the alignment material. Then, the retardation material in the desired alignment state is cured as it is, and a retardation material having a layer with optical anisotropy can be formed.

[0172] As the retardation material, for example, the liquid crystal monomer having polymerizable group and the composition containing it are used.And, in the present invention, when the substrate on which the alignment material is formed is a film, the retardation material of the present invention is useful as a retardation film.The retardation material that forms such a retardation material is in a liquid crystal state, and on the alignment material, there are some that take the alignment state such as horizontal alignment, cholesteric alignment, vertical alignment, hybrid alignment, etc., and can be used according to the retardation properties that are required.

[0173] Furthermore, when producing a patterned retardation material for use in a 3D display, the cured film on the surface of the optical film of the present invention is exposed to polarized UV light through a line-and-space pattern mask at an angle of, for example, +45 degrees from a predetermined reference, and then the mask is removed and exposed to polarized UV light at a lower exposure dose at an angle of -45 degrees. This converts the cured film on the film surface into a liquid crystal alignment film in which two types of liquid crystal alignment domains with different liquid crystal alignment control directions are formed, and the optical film can be used as an alignment material. A retardation material made of a polymerizable liquid crystal solution is then applied to the alignment material, and the retardation material is then placed in a liquid crystal state by heating to the liquid crystal phase transition temperature. The polymerizable liquid crystal in the liquid crystal state is oriented on the alignment material in which the two types of liquid crystal alignment domains are formed, forming alignment states corresponding to each of the liquid crystal alignment domains. The retardation material in this alignment state is then cured as is to fix the above-mentioned alignment state, thereby obtaining a patterned retardation material in which two types of retardation domains with different retardation characteristics are regularly arranged.

[0174] The cured film obtained using the cured film-forming composition of the present invention can also be used as a liquid crystal alignment film for a liquid crystal display element. For example, the optical film of the present embodiment formed as described above can be used to laminate two optical films together via a spacer so that the alignment materials of the two films face each other, and then a liquid crystal can be injected between the substrates to produce a liquid crystal display element in which the liquid crystal is aligned. Therefore, the cured film-forming composition of the present invention can be suitably used for producing various retardation materials (retardation films), liquid crystal display elements, etc.

[0175] EXAMPLES The present invention will be specifically described below with reference to examples of the present invention, but the present invention should not be construed as being limited to these examples.

[0176] [Abbreviations used in Examples] The meanings of the abbreviations used in the following examples are as follows: <Raw Materials> BMAA: N-butoxymethylacrylamide BMMA: N-butoxymethylmethacrylamide AAEM: (2-acetoacetoxy)ethyl methacrylate (monomer having a group represented by formula (1)) 4HBA: 4-hydroxybutyl acrylate HEMA: 2-hydroxyethyl methacrylate TGL: α-thioglycerol MAIB: 2,2'-azobis(isobutyrate) dimethyl

[0177] <Component A> MCA: 4-methoxycinnamic acid M6CA: 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid PCA: 4-propoxycinnamic acid 6CAM: 4-(6-hydroxyhexyloxy)cinnamic acid methyl ester 6MCAM: 3-methoxy-4-(6-hydroxyhexyloxy)cinnamic acid methyl ester 6BP: 4-[4-(6-hydroxyhexyloxy)benzoyl]cinnamic acid tert-butyl ester HCA: 4-hydroxycinnamic acid

[0178] <Component C> HCD: 2-hydroxypropyl-β-cyclodextrin (manufactured by CycloChem Co., Ltd., CAVASOL W7HP (registered trademark)) MCD: methyl-β-cyclodextrin (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0179] <Component D: Crosslinking catalyst> PPTS: pyridinium p-toluenesulfonate PTSA: p-toluenesulfonic acid monohydrate CSA: (±)-10-camphorsulfonic acid BSA: benzenesulfonic acid monohydrate

[0180] <Component E: Adhesion improving component> PET: Pentaerythritol triacrylate

[0181] <Other ingredients> RDK: Maximol (registered trademark) RDK-133 (Kawasaki Chemical Industries, Ltd., polyester polyol) M926: Aronix (registered trademark) M-926 (Toagosei Co., Ltd., special acrylate) HPC: Hydroxypropyl cellulose (Nippon Soda Co., Ltd., NISSO HPC SSL (registered trademark)) HMM: Hexamethoxymethylmelamine

[0182] <Solvent> PM: Propylene glycol monomethyl ether

[0183] <Measurement of weight average molecular weight> Apparatus: GPC apparatus (HLC-8320) manufactured by Tosoh Corporation Column: TSKgel (registered trademark) α-4000 and TSKgel (registered trademark) α-3000 manufactured by Tosoh Corporation Column oven: 40°C Flow rate: 1 mL / min Eluent: N,N-dimethylformamide Standard: polystyrene

[0184] Synthesis of Component B (Synthesis Example 1) BMMA (135.0 g, 789 mmol), AAEM (8.89 g, 41.5 mmol), TGL (0.898 g, 8.30 mmol) as a chain transfer agent, and MAIB (5.73 g, 24.9 mmol) as a polymerization catalyst were dissolved in PM (150.5 g), and this solution was then added dropwise over 60 minutes to a flask containing PM (200.7 g) maintained at 70°C. After completion of the addition, the mixture was allowed to react for 5 hours to obtain a solution (PB-1) (solids concentration 30% by mass) of an acrylic copolymer (BMMA / AAEM = 95 / 5 (molar ratio)). The weight-average molecular weight Mw of the resulting acrylic copolymer was 26,400.

[0185] Synthesis Example 2 BMMA (9.00 g, 52.6 mmol), AAEM (1.25 g, 5.84 mmol), TGL (63.2 mg, 0.580 mmol) as a chain transfer agent, and MAIB (0.404 g, 1.75 mmol) as a polymerization catalyst were dissolved in PM (11.2 g), and this solution was then added dropwise over 60 minutes to a flask containing PM (15.0 g) maintained at 70°C. After completion of the addition, the mixture was allowed to react for 5 hours to obtain a solution (PB-2) (solids concentration 30% by mass) of an acrylic copolymer (BMMA / AAEM = 90 / 10 (molar ratio)). The weight-average molecular weight Mw of the resulting acrylic copolymer was 26,000.

[0186] Synthesis Example 3 BMMA (7.00 g, 40.9 mmol), AAEM (3.76 g, 17.5 mmol), TGL (63.2 mg, 0.580 mmol) as a chain transfer agent, and MAIB (0.404 g, 1.75 mmol) as a polymerization catalyst were dissolved in PM (11.2 g), and this solution was then added dropwise over 60 minutes to a flask containing PM (15.0 g) maintained at 70°C. After completion of the addition, the mixture was allowed to react for 5 hours to obtain a solution (PB-3) (solids concentration 30% by mass) of an acrylic copolymer (BMMA / AAEM = 70 / 30 (molar ratio)). The weight-average molecular weight Mw of the resulting acrylic copolymer was 26,000.

[0187] Synthesis Example 4 BMMA (145.00 g, 847 mmol), TGL (0.916 g, 8.47 mmol) as a chain transfer agent, and MAIB (5.85 g, 25.4 mmol) as a polymerization catalyst were dissolved in PM (151 g), and this solution was then added dropwise over 60 minutes to a flask containing PM (202 g) maintained at 70°C. After completion of the addition, the mixture was allowed to react for 5 hours to obtain an acrylic polymer solution (PB-4) (solids concentration 30% by mass). The weight-average molecular weight Mw of the resulting acrylic copolymer was 26,400.

[0188] <Synthesis of Comparative Compound of Component C> (Synthesis Example 5) 4HBA (197.0 g, 1.37 mol) and MAIB (3.1 g, 13 mmol) as a polymerization catalyst were dissolved in PM (133.4 g), and this solution was then added dropwise over 2 hours to a flask containing PM (166.8 g) maintained at 70°C. After completion of the addition, the mixture was allowed to react for 18 hours to obtain an acrylic polymer solution (PC'-1) (solids concentration 40% by mass). The weight average molecular weight Mw of the obtained acrylic polymer was 22,700.

[0189] Synthesis Example 6 HEMA (197.0 g, 1.51 mol) and MAIB (3.5 g, 15 mmol) as a polymerization catalyst were dissolved in PM (133.7 g), and this solution was then added dropwise over 2 hours to a flask containing PM (167.1 g) maintained at 70°C. After completion of the addition, the mixture was allowed to react for 18 hours to obtain an acrylic polymer solution (PC'-2) (solids concentration 40% by mass). The weight-average molecular weight Mw of the obtained acrylic polymer was 25,000.

[0190] <Preparation of cured film-forming composition> (Example 1-1) MCA (0.1 g, 14 parts by mass) as the component (A), solution PB-1 obtained in Synthesis Example 1 (1.4 g, 60 parts by mass) as the component (B), and HCD (0.2 g, 26 parts by mass) as the component (C) were mixed, to which PM (7.3 g) as a solvent was added and stirred for 2 hours. After visually confirming dissolution, a solution was obtained. Thereafter, the resulting solution was filtered through a filter with a pore size of 0.2 μm to prepare composition (A-1) having a solids concentration of 8.0 mass%.

[0191] (Examples 1-2 to 1-36, Comparative Examples 1-1 to 1-16) (A-2) to (A-36) and (B-1) to (B-16) were prepared in the same manner as in Example 1-1, except that the types and amounts of each component shown in Table 1 below were used.

[0192] Preparation of Catalyst Solution Preparation Example 1 PPTS (1.0 g) as a catalyst and PM (19.0 g) as a solvent were added, stirred for 1 hour, and visually confirmed to be dissolved. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a catalyst solution (D-1).

[0193] Preparation Example 2: PTSA (1.0 g) as a catalyst and PM (19.0 g) as a solvent were added, stirred for 1 hour, and visually confirmed to be dissolved. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a catalyst solution (D-2).

[0194] Preparation Example 3: CSA (2.0 g) as a catalyst and PM (18.0 g) as a solvent were added, stirred for 1 hour, and visually confirmed to be dissolved. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a catalyst solution (D-3).

[0195] Preparation Example 4: BSA (1.0 g) as a catalyst and PM (19.0 g) as a solvent were added, stirred for 1 hour, and dissolved visually. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a catalyst solution (D-4).

[0196] <Preparation of liquid crystal aligning agent> (Example 2-1) To A-1 (2.00 g) obtained in Example 1-1, D-1 (0.12 g) obtained in Preparation Example 1 and PM (0.54 g) as a dilution solvent were added, and the mixture was stirred for 1 minute to obtain liquid crystal aligning agent AL-1.

[0197] (Examples 2-2 to 2-39, Comparative Examples 2-1 to 2-16) Except for using the components shown in the following Table 2, the same operation as in Example 2-1 was performed to obtain liquid crystal aligning agents (AL-2) to (AL-39), (BL-1) to (BL-16).

[0198] <Preparation of polymerizable liquid crystal solution for horizontal alignment> Paliocolor (registered trademark) LC-242 (manufactured by BASF Japan Ltd.) (19.8 g), which is a polymerizable liquid crystal for horizontal alignment, Omnirad (registered trademark) 907 (manufactured by IGM Resins B.V.) (1.0 g) as a photoradical initiator, and BYK (registered trademark)-361N (manufactured by BYK Japan KK) (0.06 g) as a leveling agent were added, and cyclopentanone (79 g) was further added as a solvent, followed by stirring for 2 hours and visually confirming that the mixture had dissolved, thereby obtaining a polymerizable liquid crystal solution (LC-1) with a solids concentration of 20% by mass.

[0199] <Formation of Liquid Crystal Alignment Film and Preparation of Retardation Film> (Example 3-1) The liquid crystal alignment agent (AL-1) obtained in Example 2-1 was applied to a TAC film substrate using a bar coater to a wet film thickness of 4 μm. The film was dried by heating at 120° C. for 2 minutes in a hot air circulation oven to form a cured film on the film. Next, linearly polarized light with a wavelength of 313 nm was applied to the surface of this cured film at 20 mJ / cm ２The liquid crystal alignment film was then vertically irradiated with an exposure dose of 400 mJ / cm. The polymerizable liquid crystal solution LC-1 for horizontal alignment was applied to the liquid crystal alignment film to a wet film thickness of 10 μm using a bar coater. The film was then dried by heating in an oven at 100°C for 2 minutes, and then irradiated with unpolarized light at a wavelength of 365 nm at a dose of 400 mJ / cm under nitrogen. ２ The polymerizable liquid crystal was cured by vertical irradiation with an exposure amount of 1000 ppm to prepare a retardation film (S-1).

[0200] (Examples 3-2 to 3-40, Comparative Examples 3-1 to 3-16) The retardation films (S-2) to (S-40), (R-1) to (R-16) were produced by carrying out the same procedure as in Example 3-1, except that the type of liquid crystal alignment agent and the type of substrate film shown in Table 3 below were changed.

[0201] The retardation films prepared above were evaluated by the following methods. The evaluation results are shown in Table 3.

[0202] [Evaluation of Liquid Crystal Alignment] The retardation films obtained in Examples 3-1 to 3-40 and Comparative Examples 3-1 to 3-16 were sandwiched between a pair of polarizing plates, and the state of expression of retardation properties under crossed Nicols was visually observed. As an evaluation standard, a film in which retardation was expressed without defects was defined as "○", and a film in which retardation was not expressed was defined as "×". The results are shown in Table 3.

[0203] [Evaluation of Liquid Crystal Repelling] The retardation films obtained in Examples 3-1 to 3-40 and Comparative Examples 3-1 to 3-16 were sandwiched between a pair of polarizing plates, and the state of expression of retardation characteristics under crossed Nicols was visually observed. Evaluation was performed by defining "○" when there was no repelling of the liquid crystal layer in the central 50 × 50 mm range, and "×" when there was repelling of the liquid crystal layer. The results are shown in Table 3.

[0204] As is clear from the results in Table 3, all of the retardation films obtained from the cured film-forming compositions containing the components (A), (B), and (C) (Examples 3-1 to 3-40) were free of liquid crystal cissing and exhibited good alignment properties. Furthermore, the retardation film obtained from the cured film-forming composition containing the components (A), (B), (C), and (E) (Example 3-40) was free of liquid crystal cissing and exhibited good alignment and adhesion. In contrast, the retardation films obtained from the cured film-forming compositions not containing the component (B) (Comparative Examples 3-1, 3-15 to 3-16) exhibited poor liquid crystal alignment properties, and the retardation films obtained from the cured film-forming compositions not containing the component (C) (Comparative Examples 3-2 to 3-14) all exhibited liquid crystal cissing, failing to produce good retardation films.

[0205] [Evaluation of Adhesion] Cross-cuts (1 mm x 1 mm x 100 squares) were made using a cutter knife on the surfaces (surfaces on which the polymerizable liquid crystal layer was formed) of the retardation films obtained in Example 3-40 and Comparative Examples 3-1 to 3-16, and then cellophane tape (Cellotape (registered trademark), 24 mm wide, manufactured by Nichiban Co., Ltd.) was applied. Next, when the cellophane tape was peeled off, the number of squares where the polymerized polymerizable liquid crystal layer remained on the underlying cured film and the underlying film substrate without peeling was counted. The evaluation was performed by defining the case where all the layer remained as "◯", the case where only a portion peeled off as "Δ", and the case where all the layer peeled off as "×". As a result, the retardation films obtained in Comparative Examples 3-1 to 3-16 were evaluated as "×", but the retardation film obtained in Example 3-40 was evaluated as "◯". It was found that the retardation films obtained from the cured film-forming compositions containing the component (E) in addition to the components (A), (B), and (C) exhibit good adhesion.

Claims

1. A composition for forming a cured film, comprising: (A) a compound having a photoalignable group; (B) a polymer having a structural unit having an N-hydroxymethyl group or an N-alkoxymethyl group; and (C) a cyclodextrin derivative in which some or all of the hydroxyl groups have been modified.

2. The cured film-forming composition according to claim 1, characterized in that the photoalignable group of component (A) is a functional group having a structure that undergoes photodimerization or photoisomerization.

3. The cured film-forming composition according to claim 1, characterized in that the photoalignable group of component (A) is a cinnamoyl group.

4. The cured film-forming composition according to claim 1, characterized in that the photoalignable group of the component (A) is a group having an azobenzene structure.

5. The composition for forming a cured film according to claim 1, wherein the component (B) is a polymer further having a structural unit having a partial structure represented by the following formula (1): (In formula (1), Q １ represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group; Q ２ is O, S or NQ ３ represents Q ３ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the dashed line represents a bond.) 6. The cured film-forming composition according to claim 1, further comprising a crosslinking catalyst as component (D).

7. The cured film-forming composition according to claim 1, further comprising an adhesion improving component as component (E).

8. An alignment material obtained by using the cured film-forming composition according to any one of claims 1 to 7.

9. A retardation material, which is formed using a cured film obtained from the cured film-forming composition according to any one of claims 1 to 7.

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