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

Abstract

[Problem] To provide a cured film-forming composition that involves the use of a film such as an acrylic film as a base material, has excellent solvent resistance, is capable of aligning a polymerizable liquid crystal with high sensitivity, and is for forming a cured film used to form an alignment material with little cissing by low-temperature firing at less than 100°C. [Solution] A cured film-forming composition containing (A) a low molecular compound having a photo-alignable group and a thermally crosslinkable group, (B) a crosslinking agent having an N-hydroxymethyl group or an N-alkoxymethyl group, (C) a polymer in which 60 mol% or more of the total repeating units include a hydroxyl group, (D) a polymer that has a repeating unit having a hydroxyl group and in which a repeating unit represented by formula (X) accounts for 45 mol% or more of the total repeating units, (E) inorganic fine particles surface-modified with a group having no (meth)acrylic groups, (F) a low molecular compound having both a (meth)acrylic group and a hydroxy group, and (G) a crosslinking catalyst. (In the formula, R1 represents a hydrogen atom or a methyl group, and R2 represents a linear or branched alkyl group having 1-5 carbon atoms.)

Description

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

[0001] The present invention relates to a cured film-forming composition for forming a cured film that aligns liquid crystal molecules, a cured film, an optical film, an alignment material, and a retardation material. In particular, the present invention relates to a patterned retardation material used in a 3D display using circularly polarized glasses, a retardation material used in a circular polarizer used as an anti-reflection film in an organic EL display, and a cured film-forming composition, a cured film, an optical film, an alignment material, and a retardation material useful for producing the retardation material.

[0002] In a 3D display using circularly polarized glasses, the alignment material is usually a retardation material disposed on a display element that forms an image, such as a liquid crystal panel. The retardation material used for this purpose has a patterned configuration in which two types of retardation regions with different retardation properties are regularly arranged in plural numbers. Hereinafter, in this specification, such a retardation material patterned to arrange multiple retardation regions with different retardation properties 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] Acrylic resins and polyimide resins having photodimerization moieties such as cinnamoyl groups and chalcone groups in their side chains are known as photoalignment materials that can be used in forming alignment materials using a photoalignment method. 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, the alignment layer is required to have solvent resistance in addition to the ability to align liquid crystals. For example, the alignment layer may be exposed to heat or solvents during the manufacturing process of the retardation material. If an alignment layer lacking solvent resistance is exposed to a solvent, the ability to align liquid crystals may be significantly reduced.

[0010] Therefore, for example, Patent Document 8 proposes a liquid crystal aligning agent containing a polymer component having a structure capable of undergoing a crosslinking reaction by light and a structure that crosslinks by heat, in order to obtain stable liquid crystal alignment ability, and a liquid crystal aligning agent containing a polymer component having a structure capable of undergoing a crosslinking reaction by light and a compound having a structure that crosslinks by heat.

[0011] In addition, the alignment layer is required to have good adhesion to the liquid crystal layer. If the adhesion between the alignment layer and the liquid crystal layer formed thereon is insufficient, the liquid crystal layer may peel off, for example, during a winding process in the production of the retardation film.

[0012] Furthermore, from the viewpoint of workability, it is required that the alignment layer can be formed by low-temperature firing at less than 100°C.

[0013] Japanese Patent Application Laid-Open No. 2005-49865 Japanese Patent Application Laid-Open No. 10-68816 U.S. Patent No. 8,119,026 Specification Japanese Patent Application Laid-Open No. 2009-179563 Japanese Patent No. 3,611,342 Japanese Patent Application Laid-Open No. 2009-058584 Japanese Patent Publication No. 2001-517719 Japanese Patent No. 4,207,430

[0014] When manufacturing retardation materials using photo-alignment technology, in recent years, in response to demands for reduced manufacturing costs, the production of optical materials using the so-called roll-to-roll method on inexpensive resin films such as acrylic film, TAC (triacetyl cellulose) film, and COP (cycloolefin polymer) film has become necessary. In particular, due to its excellent optical properties, reliability, and the advantage of being able to reduce manufacturing costs, it is desirable to use acrylic film as the resin film (substrate). However, with photo-alignment films formed from conventional materials such as those described above, the solvent resistance of the cured film formed by low-temperature baking at less than 100 ° C. is low, making it difficult to align polymerizable liquid crystals. In particular, when films such as acrylic film are used as substrates, the solvent resistance of the alignment film is low, resulting in the problem of areas that repel liquid crystals, known as repelling, and resulting in alignment defects.

[0015] Therefore, there is a need for a cured film (alignment material) that has excellent solvent resistance, can align a polymerizable liquid crystal with high sensitivity, has excellent adhesion to a liquid crystal layer and an acrylic film, and causes little repelling of the liquid crystal. Also, there is a need for a cured film-forming composition that is suitable for forming a cured film (alignment material) with such properties.

[0016] 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 that uses a film such as an acrylic film as a substrate, has excellent solvent resistance, is capable of aligning a polymerizable liquid crystal with high sensitivity, and can form a cured film used to form an alignment material with little repelling by baking at a low temperature of less than 100°C.

[0017] Another object of the present invention is 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.

[0018] Other objects and advantages of the present invention will become apparent from the following description.

[0019] Means for Solving the Problems The present inventors have conducted extensive research to solve the above problems, and as a result have found that a cured film obtained from a cured film-forming composition having a specific composition has excellent solvent resistance, is capable of aligning polymerizable liquid crystals with high sensitivity, and can be used as an alignment material that has excellent adhesion to a liquid crystal layer and an acrylic film and is less likely to repel liquid crystals, thereby completing the present invention.

[0020] That is, a first aspect of the present invention relates to a cured film-forming composition containing: (A) a low molecular weight compound having a photoalignable group and a thermally crosslinkable group; (B) a crosslinking agent having an N-hydroxymethyl group or an N-alkoxymethyl group; (C) a polymer having 60 mol % or more of all repeating units of repeating units having a hydroxy group; (D) a polymer having 45 mol % or more of all repeating units of repeating units represented by the following formula (X) and having repeating units having a hydroxy group; (E) inorganic fine particles whose surface is modified with a group not having a (meth)acrylic group; (F) a low molecular weight compound having both a (meth)acrylic group and a hydroxy group; and (G) a crosslinking catalyst. (In the above formula, R １ represents a hydrogen atom or a methyl group, R ２ represents a linear or branched alkyl group having 1 to 5 carbon atoms.

[0021] In the first aspect of the present invention, the photoalignable group of component (A) is preferably a functional group having a structure that undergoes photodimerization or photoisomerization. In the first aspect of the present invention, the photoalignable group of component (A) is preferably a cinnamoyl group or a group having an azobenzene structure. In the first aspect of the present invention, the crosslinking agent of component (B) is preferably a polymer obtained by polymerizing a monomer selected from N-hydroxymethyl(meth)acrylamide and N-alkoxymethyl(meth)acrylamide compounds.

[0022] A second aspect of the present invention relates to a cured film obtained from the cured film-forming composition of the first aspect of the present invention.

[0023] A third aspect of the present invention relates to an optical film having the cured film of the second aspect of the present invention.

[0024] A fourth aspect of the present invention relates to an alignment material formed using the cured film of the second aspect of the present invention.

[0025] A fifth aspect of the present invention relates to a retardation material formed using the cured film according to the second aspect of the present invention.

[0026] Throughout this specification, (meth)acrylic means both acrylic and methacrylic.

[0027] According to the present invention, it is possible to provide a cured film-forming composition that can form a cured film, which has excellent solvent resistance, can align a polymerizable liquid crystal with high sensitivity, and provides an alignment material with little liquid crystal repelling and excellent adhesion to a liquid crystal layer, by baking at a low temperature of less than 100° C. 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.

[0028] The cured film-forming composition of the present invention will be described in detail below, citing specific examples of components, etc. Then, the cured film and alignment material of the present invention using the cured film-forming composition of the present invention, as well as a retardation material and a liquid crystal display element, etc., formed using the alignment material will be described.

[0029] <Cured Film-Forming Composition> The cured film-forming composition of the present invention contains (A) a low molecular weight compound having a photoalignable group and a thermally crosslinkable group, (B) a crosslinking agent having an N-hydroxymethyl group or an N-alkoxymethyl group, (C) a polymer having 60 mol % or more of all repeating units containing repeating units having a hydroxy group, (D) a polymer having 45 mol % or more of all repeating units containing repeating units represented by the above formula (X) and having repeating units containing a hydroxy group, (E) inorganic fine particles surface-modified with a group not containing a (meth)acrylic group, (F) a low molecular weight compound having both a (meth)acrylic group and a hydroxy group, and (G) a crosslinking catalyst. Furthermore, other additives may be added as long as they do not impair the effects of the present invention. Furthermore, the cured film-forming composition of the present invention contains a solvent and can be in the form of a so-called varnish. Details of each component are described below.

[0030] [Component (A)] The component (A) in the cured film-forming composition of the present invention is a low molecular weight compound 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.

[0031] <Low Molecular Weight Compound Having a Photo-Alignment Group and a Thermally Crosslinkable Group> The low molecular weight compound of the component (A) is a compound having a lower molecular weight than the polymer of the component (C) described below, which serves as the base for film formation in the cured film-forming composition of the present invention, and serves as a photo-alignment component in the cured film-forming composition.

[0032] In the cured film-forming composition of the present invention, the low-molecular-weight compound of component (A) is a compound having a photoalignable group and further having a thermally crosslinkable group which is at least one group selected from the group consisting of a hydroxy group, a carboxy group, an amide group, an amino group, and an alkoxysilyl group. The photoalignable group may contain a carboxy group or an amide group.

[0033] In the present invention, the photo-alignable group generally refers to a functional group that exhibits the property of alignment upon irradiation with light, and typically refers to a functional group at a structural site that undergoes photodimerization or photoisomerization. Other photo-alignable groups include 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).

[0034] 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.

[0035] 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.

[0036] The low molecular weight compound having a photoalignable group and a thermally crosslinkable group (at least 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:

[0037]

[0038] In the above formula, A １ and A ２ each independently represents a hydrogen atom or a methyl group.

[0039] X １１ is a structure in which 1 to 3 substituents selected from an alkylene group having 1 to 18 carbon atoms, a phenylene group, a biphenylene group, or a combination 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, or a combination thereof, and a structure in which a plurality of the substituents are linked via the bond may be used.

[0040] 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, wherein two or more types of groups may be bonded to the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.

[0041] 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.

[0042] X １４represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group, where the alkylene group having 1 to 20 carbon atoms may be branched or linear.

[0043] 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.

[0044] X represents a single bond, an oxygen atom, or a sulfur atom. １４ is a single bond, then X is also a single bond.

[0045] When these substituents contain a benzene ring, 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.

[0046] 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.

[0047] Specific examples of the low molecular weight compound having a photoalignment 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 these formulas include, for example, 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-hydroxymethyloxy ... 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 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 coumarin, 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-hydroxyoctyloxycoumarin, 6-hydroxyhexyloxycoumarin, 6-(4-hydroxybutyloxy)coumarin, 6-(3-hydroxypropyloxy)coumarin, 6-(2-hydroxyethyloxy)coumarin, 6-hydroxymethyloxycoumarin, 6-hydroxycoumarin, 4-[4-(8-hydroxy 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 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-hydroxy 4-[4-(methyloxybenzoyl)]cinnamic acid tert-butyl ester, 4-[4-hydroxybenzoyl]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-hydroxybenzoyl]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-hydroxymethyloxy)benzoyl]chalcone, 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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, 4-(3-triethoxysilylhexyloxy)cinnamic acid ethyl ester, 4-(3-triethoxysilylhexyloxy)cinnamic acid ethyl ester, and 4-(3-triethoxysilylhexyloxy)cinnamic acid ethyl ester.

[0052] The low molecular weight compound of component (A) is preferably a compound in which a polymerizable group is bonded via a spacer to a group in which a photoalignable moiety and a thermally crosslinkable moiety are bonded, as represented by the following formula (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 benzene ring in these definitions may be substituted with a substituent.

[0053] When the benzene ring has 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.

[0054] R in the above formula (1) １０１ As the alkyl group, a hydroxy group and an amino group are preferred, and a hydroxy group is particularly preferred.

[0055] The spacer may be 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, the bond between the divalent groups constituting the spacer, the bond between the spacer and the group represented by the above formula (1), and the bond between the spacer and the polymerizable group may be a single bond, an ester bond, an amide bond, a urea bond, or 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.

[0056] 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 thermal crosslinking 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.

[0057] The low molecular weight photo-alignment component (A) can be exemplified by the above specific examples, but is not limited to these.

[0058] 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.

[0059] [Component (B)] The component (B) contained in the cured film-forming composition of the present embodiment is a crosslinking agent having an N-hydroxymethyl group or an N-alkoxymethyl group, and more specifically, includes an N-hydroxymethyl compound, an N-alkoxymethyl compound, or a polymer obtained by polymerizing a monomer selected from N-hydroxymethyl(meth)acrylamide and N-alkoxymethyl(meth)acrylamide compounds.

[0060] Examples of N-hydroxymethyl compounds and N-alkoxymethyl compounds include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

[0061] Specific examples of alkoxymethylated glycolurils include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.), methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins (high condensation type, trade names: Beckamin (registered trademark) J-300S, P-955, N) manufactured by DIC Corporation (formerly Dainippon Ink and Chemicals, Inc.).

[0062] Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine, etc. Commercially available products include those manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.) (trade name: Cymel (registered trademark) 1123) and those manufactured by Sanwa Chemical Co., Ltd. (trade names: Nikalac (registered trademark) BX-4000, BX-37, BL-60, BX-55H).

[0063] Specific examples of alkoxymethylated melamine include hexamethoxymethyl melamine, etc. Commercially available products include methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) and butoxymethyl type melamine compounds (trade names: Mycoat (registered trademark) 506, 508) manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.), and methoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, MX-035) and butoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MX-45, MX-410, MX-302) manufactured by Sanwa Chemical Co., Ltd.

[0064] The compound may also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, or a benzoguanamine compound in which the hydrogen atom of the amino group has been substituted with a methylol group or an alkoxymethyl group. Examples include high-molecular-weight compounds produced from melamine compounds and benzoguanamine compounds described in U.S. Patent No. 6,323,310. Commercially available melamine compounds include Cymel (registered trademark) 303, and commercially available benzoguanamine compounds include Cymel (registered trademark) 1123 (both manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.)).

[0065] Examples of polymers obtained by polymerizing a monomer selected from N-hydroxymethyl(meth)acrylamide and N-alkoxymethyl(meth)acrylamide compounds include polymers obtained by polymerizing a monomer such as N-alkoxymethyl(meth)acrylamide or N-hydroxymethyl(meth)acrylamide alone or copolymerized with a copolymerizable monomer. Examples of such polymers include poly(N-butoxymethylacrylamide), poly(N-ethoxymethylacrylamide), poly(N-methoxymethylacrylamide), poly(N-hydroxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-butoxymethylacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate. The weight-average molecular weight of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 50,000. The weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard. The same applies hereinafter in this specification.

[0066] These crosslinking agents of component (B) may be used singly or in combination of two or more.

[0067] The content of the crosslinking agent having an N-hydroxymethyl group or an N-alkoxymethyl group as component (B) in the cured film-forming composition of the present embodiment is preferably 100 to 2,000 parts by mass, and more preferably 200 to 1,500 parts by mass, based on 100 parts by mass of the compound as component (A).

[0068] [Component (C)] The component (C) contained in the cured film-forming composition of the present invention is a polymer (hereinafter also referred to as specific polymer C) having, as a unit structure, repeating units having a hydroxy group in an amount of 60 mol % or more of all repeating units.

[0069] Examples of the polymer that is the component (C) include polymers having a linear or branched chain structure, such as acrylic polymers, urethane-modified acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, polyalkyleneimines, polyallylamine, celluloses (cellulose or derivatives thereof), and phenol novolac resins, and cyclic polymers, such as cyclodextrins.

[0070] Among these, the acrylic polymer may be a polymer obtained by (co)polymerizing an acrylic acid ester, a methacrylic acid ester, or a monomer having an unsaturated double bond such as styrene. A convenient method for synthesizing the acrylic polymer is to (co)polymerize a monomer having a hydroxy group and, if desired, other monomers.

[0071] Examples of monomers having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2-(acryloyloxy)ethyl 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.

[0072] Of these, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate are particularly preferred.

[0073] In the cured film-forming composition of the present invention, when obtaining the specific polymer C, a monomer copolymerizable with the monomer having a hydroxy group (hereinafter also referred to as a monomer having a non-reactive functional group) can be used in combination.

[0074] Specific examples of such monomers having a non-reactive functional group 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 monomers having the non-reactive functional group are listed below, but the present invention is not limited to these.

[0075] Examples of the acrylic acid ester compounds include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl 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.

[0076] Examples of the methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl 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.

[0077] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0078] Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

[0079] 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.

[0080] The method for obtaining the specific polymer C used in the cured film-forming composition of the present invention is not particularly limited, and examples thereof include a method of carrying out a polymerization reaction at a temperature of 50° C. to 110° C. in a solvent in which a monomer having a hydroxy group, an optional monomer having a non-reactive functional group, a polymerization initiator, etc. are present together. The solvent used in this case is not particularly limited as long as it dissolves the monomer having a hydroxy group, the optional monomer having a non-reactive functional group, the polymerization initiator, etc. Specific examples include the solvents described in [Solvent] below.

[0081] The specific polymer C 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 (C) in the present invention.

[0082] Alternatively, the solution of specific polymer C 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 or reduced pressure to obtain a powder of specific polymer C. By such an operation, the polymerization initiator and unreacted monomers coexisting with specific polymer C can be removed, resulting in a powder of purified specific polymer C. If sufficient purification cannot be achieved by a single operation, the obtained powder can be redissolved in a solvent, and the above operation can be repeated.

[0083] In the cured film-forming composition of the present invention, the powder of the specific polymer C may be used as it is as the polymer of component (C), or the powder may be redissolved in, for example, a solvent described below and used in the form of a solution.

[0084] The acrylic polymer, which is an example of component (C), preferably has a weight-average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and even more preferably 5,000 to 100,000. If the weight-average molecular weight is too high, exceeding 200,000, the solubility in solvents may decrease, resulting in poor handling, while if the weight-average molecular weight is too low, less than 3,000, the polymer may not cure sufficiently during heat curing, resulting in poor solvent resistance and heat resistance.

[0085] In the composition of the present invention, the component (C) may be a mixture of two or more of the polymers exemplified as the component (C).

[0086] The amount of component (C) in the cured film-forming composition of the present invention is 50 to 1,500 parts by mass, preferably 100 to 1,000 parts by mass, and more preferably 200 to 500 parts by mass, based on 100 parts by mass of component (A).

[0087] [Component (D)] The component (D) contained in the cured film-forming composition of the present invention is a polymer (hereinafter also referred to as specific copolymer D) having repeating units represented by the following formula (X) in an amount of 45 mol % or more of all repeating units and having a repeating unit having a hydroxy group: (In the above formula, R １ represents a hydrogen atom or a methyl group, R ２ represents a linear or branched alkyl group having 1 to 5 carbon atoms.) Hereinafter, a monomer that provides a repeating unit represented by the above formula (X) will be referred to as specific monomer X.

[0088] Examples of the alkyl acrylate or alkyl methacrylate monomer that is the specific monomer X include alkyl acrylate compounds such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate, and alkyl methacrylate compounds such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate.

[0089] Among these specific monomers X, methyl methacrylate is particularly preferred from the viewpoints of availability and affinity with the acrylic film used as the substrate. That is, the component (D) is a polymer obtained by using methyl methacrylate as a monomer, that is, in the formula (X), R １ and R ２is preferably a polymer having a unit structure in which all of the units represent a methyl group.

[0090] The specific copolymer D, which is the component (D), may be a polymer obtained by polymerizing the specific monomer X, such as an alkyl acrylate or alkyl methacrylate, as well as a monomer having an unsaturated double bond, such as styrene.

[0091] Furthermore, the component (D) is preferably an acrylic copolymer obtained by copolymerizing the specific monomer X, ie, an alkyl acrylate or alkyl methacrylate, with a monomer having a hydroxy group.

[0092] As a method for synthesizing an acrylic copolymer in which a monomer having a hydroxy group is further copolymerized in addition to the specific monomer X, which is an alkyl acrylate or alkyl methacrylate ester, a method in which the specific monomer X is copolymerized with at least one monomer selected from monomers having a hydroxy group is simple.

[0093] Examples of monomers having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 8-hydroxyoctyl acrylate, 8-hydroxyoctyl methacrylate, 10-hydroxydecyl acrylate, 10-hydroxydecyl 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, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and the like.

[0094] Of these, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate are particularly preferred.

[0095] Furthermore, in the present invention, when obtaining the specific copolymer D, in addition to the specific monomer X and the monomer having a hydroxy group, a monomer copolymerizable with the specific monomer X and not having the crosslinkable group (other monomer) can be used in combination.

[0096] Specific examples of such other monomers include specific monomer X, and acrylic acid ester compounds or methacrylic acid ester compounds having a structure different from that of the monomer having a hydroxy group, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

[0097] Specific examples of the other monomers include, but are not limited to, the following: acrylic acid ester compounds having a structure different from that of the specific monomer X, etc., include benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl 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.

[0098] Examples of methacrylic acid ester compounds having a structure different from the specific monomer X and the like include benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl 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.

[0099] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0100] Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

[0101] Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, allyl glycidyl ether, phenyl vinyl ether, propyl vinyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0102] In the polymer of component (D), the proportion of the unit structure represented by formula (X) is preferably 45 mol% to 95 mol%, more preferably 55 mol% to 90 mol%, and even more preferably 70 mol% to 90 mol%, based on the total amount of the polymer. That is, the amount of specific monomer X used to obtain specific copolymer D of component (D) is preferably 45 mol% to 95 mol%, more preferably 55 mol% to 90 mol%, and even more preferably 70 mol% to 90 mol%, based on the total amount of all monomers used to obtain specific copolymer D of component (D).

[0103] Furthermore, from the viewpoint of strengthening the adhesion between the film and the substrate through sufficient reaction with the component (B), the total amount of the hydroxyl group-containing monomers used in the component (D) is preferably 5 mol % to 30 mol % based on the total amount of all monomers used to obtain the specific copolymer D, which is the component (D).

[0104] The method for obtaining the specific copolymer D, which is an example of the component (D), is not particularly limited, but for example, it can be obtained by a polymerization reaction at a temperature of 50° C. to 130° C. in a solvent containing the specific monomer X, a monomer having a hydroxy group, and optionally other monomers (other monomers), a polymerization initiator, etc. In this case, the solvent used is not particularly limited as long as it dissolves the monomer represented by the above formula X, the monomer having a hydroxy group, optionally other monomers (other monomers), the polymerization initiator, etc. Specific examples of the solvent used in the polymerization reaction are described in the section [Solvent] below.

[0105] The acrylic polymer, which is an example of component (D), obtained by the above method is usually in the form of a solution dissolved in a solvent, and can be used as is as the solution of component (D) in the present invention.

[0106] Furthermore, the solution of the acrylic polymer, an example of component (D) obtained by the above method, can be reprecipitated by adding it to 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 or reduced pressure to obtain a powder of specific copolymer D, component (D). The above-mentioned operation can remove the polymerization initiator and unreacted monomers coexisting with specific copolymer D, component (D), and as a result, a purified powder of specific copolymer D, an example of component (D), can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder can be redissolved in a solvent, and the above-mentioned operation can be repeated.

[0107] In the cured film-forming composition of the present invention, the specific copolymer D of the component (D) may be used in the form of a powder or in the form of a solution obtained by redissolving the purified powder in a solvent described below.

[0108] Furthermore, in the cured film-forming composition of the present invention, the component (D) may be a mixture of multiple types of specific copolymer D, which is exemplified as the component (D). The acrylic polymer, which is an example of the component (D), preferably has a weight-average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and even more preferably 5,000 to 100,000. If the weight-average molecular weight is too high, exceeding 200,000, the solubility in solvents may decrease, resulting in poor handleability. If the weight-average molecular weight is too low, less than 3,000, the polymer may not be sufficiently cured during heat curing, resulting in poor solvent resistance and heat resistance.

[0109] The content of the component (D) in the cured film-forming composition of the present invention is preferably 10 to 500 parts by mass, more preferably 20 to 300 parts by mass, and even more preferably 30 to 200 parts by mass, based on 100 parts by mass of the low molecular weight compound having a photoalignable group and a thermally crosslinkable group, which is the component (A).

[0110] [Component (E)] The component (E) contained in the cured film-forming composition of this embodiment is inorganic fine particles surface-modified with a group not having a (meth)acrylic group. Examples of inorganic fine particles for component (E) include silica particles having a primary particle diameter of 1 nm to 200 nm and surface-modified with a group not having a (meth)acrylic group. In particular, from the viewpoint of the storage stability of the varnish, silica particles surface-modified with at least one silane coupling agent are preferred. Furthermore, from the viewpoint of not affecting the liquid crystal alignment, silica particles having a primary particle diameter of 1 nm to 100 nm or 20 nm to 100 nm and surface-modified with a silane coupling agent are preferred.

[0111] The silane coupling agent that modifies the surface of the silica particles as component (E) of the cured film-forming composition of the present invention may be any silane coupling agent that does not have a (meth)acrylic group, and examples thereof include methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, n-pentyltrimethoxysilane, cyclopentyltrimethoxysilane, n-hexyltrimethoxysilane, cyclohexyltrimethoxysilane, isooctyltrimethoxysilane, phenyltrimethoxysilane, ... methyltrimethoxysilane, methyltrimethoxysilane, methyltrimethoxysilane, methyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, n-pentyltrimethoxysilane, cyclopentyltrimethoxysilane, methyltrimethoxysilane, methyltrimethoxysilane, methyltrimethoxysilane, isopropyltrimethoxysilane Trimethoxysilane, p-tolyltrimethoxysilane, benzyltrimethoxysilane, 1-naphthyltrimethoxysilane, trimethoxy[3-(phenylamino)propyl]silane, [3-(N,N-dimethylamino)propyl]trimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 8-(2-aminoethylamino)octyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, tris[3-(trimethoxysilyl ) propyl] isocyanurate, methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane, n-pentyltriethoxysilane, cyclopentyltriethoxysilane, n-hexyltriethoxysilane, cyclohexyltriethoxysilane, isooctyltriethoxysilane, phenyltriethoxysilane, p-tolyltriethoxysilane, benzyltriethoxysilane, 3-aminopropyltriethoxysilane, 3 trialkoxysilanes such as 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, and tris[3-(triethoxysilyl)propyl]isocyanurate; dimethyldimethoxysilane, diethyldimethoxysilane, diisobutyldimethoxysilane, cyclopentylmethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, di-p-tolyldimethoxysilane, and 3-aminopropylmethyldimethoxysilane;Examples of suitable silane coupling agents include dialkoxysilanes such as 3-mercaptopropylmethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diisobutyldiethoxysilane, cyclopentylmethyldiethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldiethoxysilane, phenylmethyldiethoxysilane, diphenyldiethoxysilane, di-p-tolyldiethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 3-mercaptopropylmethyldiethoxysilane; monoalkoxysilanes such as trimethylmethoxysilane, triethylmethoxysilane, phenyldimethylmethoxysilane, diphenylmethylmethoxysilane, and triphenylmethoxysilane; and polyfunctional silane coupling agents.

[0112] The silane coupling agents can be used alone or in combination of two or more.

[0113] When surface-modifying silica particles using a silane coupling agent, the amount of the silane coupling agent used is preferably 0.1 to 2.0 mmol, more preferably 0.5 to 2.0 mmol, and even more preferably 0.5 to 1.7 mmol per 1 g of the silica particles.

[0114] By using an amount of silane coupling agent greater than 0.1 millimoles, the affinity and adhesion between the surface of the silica particles and the organic resin are sufficient, the transmittance of the cured product and molded article obtained from the cured film-forming composition of the present invention is not reduced, and cracks can be prevented from occurring at the base of the cured product and molded article after the development process using an organic solvent.By using an amount of silane coupling agent less than 2.0 millimoles, the silane coupling agent is not excessive relative to the silica particles, and no silane coupling agent is left unused for surface modification of the silica particles, allowing the storage stability and mechanical properties of the cured product and molded article to be maintained.

[0115] In the cured film-forming composition of the present invention, the silica particles of component (E) have a primary particle diameter of, for example, 1 nm to 200 nm. Here, primary particles are particles that constitute a powder, and particles formed by aggregation of these primary particles are called secondary particles. The primary particle diameter can be calculated from the relationship D = 6 / (ρS) that holds between the specific surface area (surface area per unit mass) S of the silica particles measured by gas adsorption (BET) method, the density ρ of the silica particles, and the primary particle diameter D. The primary particle diameter calculated from the relationship is the average particle diameter, i.e., the diameter of the primary particles. Using particles with a primary particle diameter greater than 1 nm can suppress aggregation of the silica particles, thereby improving storage stability. Using particles with a primary particle diameter smaller than 200 nm can improve the transparency of the cured product and molded article.

[0116] The silica particles of component (E) can be obtained by reacting surface-unmodified silica particles with the silane coupling agent by various known methods. As the surface-unmodified silica particles, for example, it is preferable to use the silica particles dispersed in an organic solvent (organosilica sol).

[0117] The organosilica sol may be a commercially available water-dispersed silica sol in which the water is replaced with an organic solvent by a known method such as vacuum distillation or ultrafiltration, or a commercially available powdered silica particle dispersed in an organic solvent.

[0118] The silica solid content concentration in the organosilica sol is not particularly limited, but is generally preferably 60% by mass or less.

[0119] The content of component (E) in the cured film-forming composition of the present invention is preferably 3 to 60 parts by mass, more preferably 3 to 45 parts by mass, and even more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the total amount of components (A), (B), (C), (D), and (F) described below contained in the cured film-forming composition. If the content of component (E) is less than 3 parts by mass, the heat resistance of the cured product and molded article obtained from the cured film-forming composition may be deteriorated. If the content of component (E) is more than 60 parts by mass, haze may occur in the cured product and molded article, and the transmittance may be reduced.

[0120] The component (E) may be used singly or in combination of two or more. For example, a plurality of silica particles having different primary particle sizes may be combined, or a plurality of silica particles having different types or amounts of silane coupling agents used for surface modification may be combined.

[0121] [Component (F)] The component (F) contained in the cured film-forming composition of the present embodiment is a compound having a hydroxy group and a (meth)acrylic group.

[0122] The compound of component (F) preferably has one or more hydroxy groups and one or more (meth)acrylic groups.

[0123] When the cured film formed from the cured film-forming composition of the present embodiment containing the component (F) is used as an alignment material, the polymerizable functional group of the polymerizable liquid crystal and the cross-linking reaction site of the alignment material can be linked by a covalent bond so as to improve the adhesion between the alignment material and the polymerizable liquid crystal layer. As a result, the retardation material of the present embodiment, which is 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 humidity conditions and can exhibit high durability against peeling, etc.

[0124] The content of the component (F) in the cured film-forming composition of the present embodiment is preferably 1 to 150 parts by mass, and more preferably 1 to 70 parts by mass, based on 100 parts by mass of the low molecular weight compound having a photoalignable group and a thermally crosslinkable group, which is the component (A).

[0125] In the cured film-forming composition of the present embodiment, the component (F) may be a mixture of multiple types of compounds of the component (F).

[0126] Preferred examples of the compound of component (F) are listed below: However, the compound of component (F) is not limited to the following compound examples.

[0127] (In the above formula, R １１１ represents a hydrogen atom or a methyl group, and s represents an integer of 1 to 10. m, n, o, p, q, and r each independently represent an integer of 0 to 6.

[0128] [Component (G)] The cured film-forming composition of the present invention further contains a crosslinking catalyst as component (G), in addition to the above-described components (A), (B), (C), (D), (E), and (F).

[0129] Examples of the crosslinking catalyst as component (G) include an acid or a thermal acid generator. This component (G) is effective in promoting the thermal curing reaction when a cured film is formed from the cured film-forming composition of the present invention (i.e., the composition that forms the cured film on the surface of the optical film of the present invention, which will be described later).

[0130] When an acid or thermal acid generator is used as component (G), component (G) 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 undergoes thermal decomposition during pre-baking or post-baking to generate an acid, i.e., a compound that undergoes thermal decomposition at a temperature of 60°C to 250°C to generate an acid.

[0131] 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.

[0132] Examples of the compound that generates an acid by heat (by thermal decomposition) 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 morpholinium 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-tosylate, N-ethyl-4-toluenesulfonamide, and the compounds represented by the following formulae [TAG-1] to [TAG-41].

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140] The component (G) 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.).

[0141] The content of the component (G) in the cured film-forming composition of the present invention is preferably 0.01 to 100 parts by mass, more preferably 1 to 100 parts by mass, even more preferably 10 to 100 parts by mass, and particularly preferably 20 to 80 parts by mass, per 100 parts by mass of the component (A). By ensuring that the content of the component (G) 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 100 parts by mass or less, the storage stability of the cured film-forming composition can be improved.

[0142] [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.

[0143] 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.

[0144] These sensitizers are not particularly limited to those mentioned above, and these can be used alone or in combination of two or more compounds.

[0145] In an embodiment of the present invention, when a sensitizer is used, the proportion used is preferably 1 to 100 parts by mass, and more preferably 10 to 80 parts by mass, per 100 parts by mass of component (A). If this proportion is too small, the effect of the 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.

[0146] The cured film-forming composition according to an embodiment of the present invention may 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.

[0147] [Solvent] The cured film-forming composition according to the embodiment of the present invention can be used in the form of a solution dissolved in a solvent. The solvent used in this case dissolves the components (A), (B), (C), (D), (E), (F), and (G), as well as other additives as necessary. The type and structure of the solvent are not particularly limited as long as it has the ability to dissolve the components.

[0148] 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, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, 2-methyl-2-pent ... ethanol, 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, methanol, ethanol, n-propanol, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

[0149] 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.).

[0150] 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.

[0151] <Preparation of Cured Film-Forming Composition> The cured film-forming composition of the present invention (i.e., the composition that forms the cured film on the surface of the optical film of the present invention) comprises, as described above, component (A) a low molecular weight compound having a photoalignment group and a thermally crosslinkable group (photoalignment component), component (B) a crosslinking agent having an N-hydroxymethyl group or an N-alkoxymethyl group, component (C) a polymer having 60 mol % or more of all repeating units of repeating units having a hydroxy group, component (D) a polymer having 45 mol % or more of all repeating units of repeating units represented by formula (X) and having repeating units having a hydroxy group, component (E) inorganic fine particles that are surface-modified with a group that does not have a (meth)acrylic group, component (F) a low molecular weight compound having both a (meth)acrylic group and a hydroxy group, and component (G) a crosslinking catalyst, and in one embodiment, can further contain a solvent, so that each of the above-mentioned components is dissolved in the solvent. The cured film-forming composition of the present invention can also contain other additives as long as the effects of the present invention are not impaired.

[0152] Preferred examples of the cured film-forming composition of the present invention are as follows.

[0153] a cured film-forming composition comprising: component (A); 100 parts by mass to 2,000 parts by mass of component (B) based on 100 parts by mass of the compound that is component (A); 50 parts by mass to 1,500 parts by mass of component (C) based on 100 parts by mass of component (A); 10 parts by mass to 500 parts by mass of component (D) based on 100 parts by mass of the low molecular weight compound that has a photoalignable group and a thermally crosslinkable group that is component (A); 3 parts by mass to 60 parts by mass of component (E) based on 100 parts by mass of the total amount of components (A), (B), (C), (D), and (F); 1 part by mass to 150 parts by mass of component (F) based on 100 parts by mass of component (A); 0.01 parts by mass to 100 parts by mass of component (G) based on 100 parts by mass of component (A); and a solvent.

[0154] The blending ratios, preparation methods, etc., when the cured film-forming composition of the present invention is used as a solution (in the form of a so-called varnish) 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 preferably 1 to 80% by mass, more preferably 2 to 60% by mass, and even more preferably 3 to 40% by mass. Here, the solid content refers to all components of the cured film-forming composition excluding the solvent.

[0155] 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 components (A), (B), (C), (E), (F), and (G) are mixed in a predetermined ratio with a solution of component (D) dissolved in a solvent to obtain 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. Furthermore, component (G) may be added immediately before use in order to enhance the storage stability of the varnish.

[0156] In preparing the cured film-forming composition of the present invention, as described above, a solution of specific copolymer D (component (D)) obtained by polymerization in a solvent can be used as is. In this case, for example, components (A), (B), (C), (E), (F), etc. are added to a solution of component (D) obtained by copolymerizing the aforementioned monomer having a hydroxy group, monomer X, 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 (D) and the solvent used to adjust the concentration of the cured film-forming composition may be the same or different.

[0157] 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.

[0158] <Optical Film> The optical film of the present invention is preferably obtained by applying the above-mentioned cured film-forming composition (a solution thereof) onto a film (for example, a resin film such as a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, or an acrylic film) substrate by bar coating, spin coating, flow coating, roll coating, slit coating, spin coating followed by slit coating, 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.

[0159] As the acrylic film, a film made of a copolymer containing alkyl methacrylate and / or alkyl acrylate as the main monomer component can be suitably used.

[0160] The film used as the substrate preferably has a thickness of 20 μm to 100 μm.

[0161] The heating and drying conditions are such that, when a cured film is used as a liquid crystal alignment film as described below, 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 99°C and 0.4 to 60 minutes are used. The heating temperature and heating time are preferably 60°C to 95°C and 0.5 to 10 minutes.

[0162] The thickness of the cured film on the surface of the optical film of the present invention is, for example, 0.05 μm to 10 μm, and can be appropriately selected in consideration of the step and optical and electrical properties of the film used as the substrate.

[0163] The optical film of the present invention produced in this manner 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., as a component for aligning compounds having liquid crystal properties, including polymerizable liquid crystals, etc., and therefore the optical film can be used as an alignment material.

[0164] 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.

[0165] 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, which can be aligned on the alignment material. Then, by curing the retardation material in the desired alignment state as it is, a retardation material having a layer with optical anisotropy can be formed.

[0166] 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, since the substrate of the alignment material is a film, the retardation material of the present invention is useful as a retardation film.The retardation material forming 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 required.

[0167] 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 angle of -45 degrees. This allows the cured film on the film surface to be converted 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 converted into an alignment material in which two types of liquid crystal distribution domains are formed. A retardation material made of a polymerizable liquid crystal solution is then applied to the alignment material, and the retardation material is then converted into 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 oriented state is then cured as is, and the above-mentioned alignment state is fixed, thereby obtaining a patterned retardation material in which two types of retardation domains with different retardation characteristics are regularly arranged.

[0168] The optical film 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 optical film of the present invention can be suitably used for producing various retardation materials (retardation films), liquid crystal display elements, etc.

[0169] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0170] [Abbreviations used in Examples] The meanings of the abbreviations used in the following examples are as follows.

[0171] <Raw materials> BMAA: N-butoxymethylacrylamide 4HBA: 4-hydroxybutyl acrylate MMA: methyl methacrylate AIBN: α,α'-azobisisobutyronitrile MAIB: 2,2'-azobis(isobutyric acid) dimethyl

[0172] <Solvent> PM: Propylene glycol monomethyl ether MEK: Methyl ethyl ketone IPM: Neoethanol (registered trademark) IPM (manufactured by Taishin Chemical Co., Ltd.) EA: Ethyl acetate CPN: Cyclopentanone

[0173] <Component (A): low molecular weight compound having a photoalignable group and a thermally crosslinkable group> M6CA:

[0174] 6CAM:

[0175] <Inorganic fine particle components> E-1 (alkylsilyl-modified organosilica sol) (corresponding to component (E)) E-2 (organosilica sol having a (meth)acrylic group) E-3 (organosilica sol having a (meth)acrylic group)

[0176] <Component (F): Low-molecular-weight compound having both a (meth)acrylic group and a hydroxy group> PE-200: Blemmer (registered trademark) PE-200 (manufactured by NOF Corporation) (polyethylene glycol monomethacrylate) CHDMMA: 1,4-cyclohexanedimethanol monoacrylate (manufactured by Shinryo Corporation)

[0177] <Component (G): Crosslinking catalyst> CSA: (±)-10-camphorsulfonic acid

[0178] <Measurement of weight average molecular weight> Apparatus: GPC apparatus (HLC-8320) manufactured by Tosoh Corporation Column: Shodex (registered trademark) Asahipak GF-310HQ, GF-510HQ, and GF-710HQ manufactured by Showa Denko K.K. Column oven: 40°C Flow rate: 0.6 ml / min Eluent: N,N-dimethylformamide Standard sample: polystyrene

[0179] <Synthesis of Component (B)> <Synthesis Example 1> BMAA (145.5 g) and AIBN (4.6 g) as a polymerization catalyst were dissolved in PM (150.1 g), and this solution was then added dropwise over 30 minutes to a flask containing PM (200.1 g) maintained at 80°C. After completion of the addition, the mixture was allowed to react at 80°C for 5 hours to obtain an acrylic polymer solution (PB-1) (solids concentration 30% by mass). The weight average molecular weight Mw of the obtained acrylic polymer was 23,000.

[0180] <Synthesis of Component (C)> <Synthesis Example 2> 4HBA (197.0 g) and MAIB (3.1 g) 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 at 70°C 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.

[0181] <Synthesis of Component (D)> <Synthesis Example 3> MMA (84.4 g), 4HBA (13.5 g), and MAIB (2.2 g) as a polymerization catalyst were dissolved in PM (150.1 g), and this solution was then added dropwise over 2 hours to a flask containing PM (250.2 g) maintained at 70°C. After completion of the addition, the mixture was allowed to react at 70°C for 18 hours to obtain an acrylic copolymer solution (PD-1) (solids concentration 20% by mass). The weight average molecular weight Mw of the obtained acrylic copolymer was 38,900.

[0182] <Preparation of Composition> <Preparation Example 1> (A) M6CA (0.080 g) as component, (B) 30 mass% PM solution of the acrylic polymer obtained in Synthesis Example 1 (PB-1) (1.093 g) as component, (C) 40 mass% PM solution of the acrylic polymer obtained in Synthesis Example 2 (PC-1) (0.520 g) as component, (D) 20 mass% PM solution of the acrylic copolymer obtained in Synthesis Example 3 (PD-1) (0.400 g) as component, (E) E-1 (0.267 g) as component, (F) PE-200 (0.024 g), and PM (7.614 g) were added, stirred for 2 hours, and dissolution was confirmed visually. Thereafter, by filtration through a glass filter having a pore size of 1.0 μm, a composition (A-1) having a solids concentration of 8.0 mass% was prepared.

[0183] Preparation Examples 2 to 8 Compositions (A-2) to (A-4) and (C-1) to (C-5) were prepared in the same manner as in Preparation Example 1, except that the types and amounts of each component shown in Table 1 below were used.

[0184]

[0185] In Table 1, the numbers in parentheses for components (A) to (F) and other components indicate the mass ratio of each component (excluding the amount of solvent if diluted with a solvent).

[0186] <Preparation of Crosslinking Catalyst Solution> <Preparation Example 10> CSA (2.0 g) as a crosslinking 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 crosslinking catalyst solution (G-1).

[0187] Preparation Example 11 Preparation of Polymerizable Liquid Crystal Solution for Horizontal Alignment Paliocolor (registered trademark) LC-242 (manufactured by BASF Japan Ltd.) (19.3 g), which is a polymerizable liquid crystal for horizontal alignment, Omnirad (registered trademark) 907 (manufactured by IGM Resins BV (formerly BASF Japan Ltd.)) (0.6 g) as a photoradical initiator, and BYK (registered trademark)-361N (manufactured by BYK Japan KK) (0.1 g) as a leveling agent were added, and CPN (80 g) was further added as a solvent. The mixture was stirred for 2 hours, and dissolution was confirmed visually. The mixture was then filtered through a PTFE filter having a pore size of 0.2 μm, thereby obtaining a 20% by mass polymerizable liquid crystal solution (LC-1).

[0188] <Preparation of Cured Film-Forming Composition> <Example 1-1> A-1 (2.00 g) obtained in Preparation Example 1, G-1 (0.08 g) obtained in Preparation Example 10, EA (0.90 g) as a dilution solvent, and IPM (0.90 g) were added and stirred for 15 hours to obtain a cured film-forming composition (AL-1).

[0189] Examples 1-2 to 1-4 Cured film-forming compositions (AL-2) to (AL-4) were obtained in the same manner as in Example 1-1, except that A-2 to A-4 were used instead of A-1.

[0190] Comparative Examples 1-1 to 1-5 Cured film-forming compositions CL-1 to CL-5 were obtained in the same manner as in Example 1-1, except that C-1 to C-5 were used instead of A-1.

[0191] <Formation of Liquid Crystal Alignment Film and Preparation of Retardation Film> <Example 2-1> The cured film-forming composition (AL-1) obtained in Example 1-1 was applied to an acrylic film substrate using a bar coater to a wet film thickness of 6 μm. The film was dried by heating at 90°C for 1 minute in a heat circulation oven to form a cured film on the film. Next, linearly polarized light with a wavelength of 313 nm was applied at 20 mJ / cm on the surface of this cured film. ２The liquid crystal alignment film was then vertically irradiated with an exposure dose of 100 mJ / cm. A polymerizable liquid crystal solution LC-1 for horizontal alignment was applied to the liquid crystal alignment film to a wet thickness of 8 μm using a bar coater. The film was then dried by heating in an oven at 90°C for 1 minute, and then irradiated with unpolarized light at a wavelength of 365 nm at a dose of 500 mJ / cm under a nitrogen atmosphere. ２ The polymerizable liquid crystal was cured by vertical irradiation with an exposure amount of 1000 ppm to prepare a retardation film (S-1).

[0192] Examples 2-2 to 2-4, Comparative Examples 2-1 to 2-5 Retardation films (S-2) to (S-4) and (R-1) to (R-5) were produced as shown in the table below by performing the same procedure as in Example 2-1, except that AL-2 to AL-4 or CL-1 to CL-5 were used instead of the cured film-forming composition AL-1.

[0193] [Evaluation of Orientation] The retardation films S-1 to S-4 and R-1 to R-5 obtained in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-5 were sandwiched between a pair of polarizing plates, and the state of expression of retardation properties under crossed Nicols was visually observed. Those in which retardation was expressed without defects were evaluated as "A", and those in which retardation was not expressed were evaluated as "C". The results are shown in Table 3.

[0194] [Evaluation of repelling] The retardation films S-1 to S-4 and R-1 to R-5 obtained in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-5 were sandwiched between a pair of polarizing plates, and the state of expression of retardation characteristics under crossed Nicols was visually observed. The film was evaluated as "A" when there was no repelling of the liquid crystal layer in the central 50 × 50 mm range, as "B" when there were several to 20 repellings of the liquid crystal layer, and as "C" when there were more than 20 repellings of the liquid crystal layer. The results are shown in Table 3.

[0195] [Adhesion Evaluation] Using a cutter knife, 100 squares were cut into the prepared retardation film on the substrate at 1 mm intervals in a grid pattern, and Cellotape (registered trademark) (manufactured by Nichiban Co., Ltd., 24 mm width) was firmly pressed onto the film and then peeled off in one go to measure the number of grids remaining on the substrate. The case where all the grids remained was evaluated as "A", the case where some of the grids peeled off was evaluated as "B", and the case where all the grids peeled off was evaluated as "C". The results are shown in Table 3.

[0196] As is clear from the results in Table 3, none of the retardation films obtained in Examples 2-1 to 2-4 exhibited cissing and showed good alignment. Furthermore, it can be seen that they had good adhesion to the liquid crystal and the substrate. In contrast, Comparative Examples 2-1 to 2-5 did not produce good retardation films that satisfied all of the properties of alignment, cissing, and adhesion. By using inorganic fine particles surface-modified with a group that does not have a (meth)acrylic group as component (E), interaction with the low-molecular-weight compound (F) that has both a (meth)acrylic group and a hydroxyl group is suppressed, resulting in component (F) being ubiquitous on the surface and not interfering with its function as an adhesion promoter, and therefore, it is believed that an alignment material with high adhesion to the liquid crystal layer can be obtained.

[0197] The film having the cured film formed thereon according to the present invention is very useful as a liquid crystal alignment material for liquid crystal display elements or as an alignment material for forming optically anisotropic films provided inside or outside liquid crystal display elements, and is particularly suitable as a material for forming patterned retardation materials for 3D displays.Furthermore, it is also suitable as a material for forming cured films such as protective films, planarizing films, and insulating films in various displays such as thin film transistor (TFT) liquid crystal display elements and organic EL elements, and is particularly suitable as a material for forming interlayer insulating films in TFT liquid crystal elements, protective films in color filters, or insulating films in organic EL elements.

Claims

1. A cured film-forming composition comprising: (A) a low molecular weight compound having a photoalignable group and a thermally crosslinkable group; (B) a crosslinking agent having an N-hydroxymethyl group or an N-alkoxymethyl group; (C) a polymer having 60 mol % or more of all repeating units of repeating units having a hydroxy group; (D) a polymer having 45 mol % or more of all repeating units of repeating units represented by the following formula (X) and having repeating units having a hydroxy group; (E) inorganic fine particles whose surface is modified with a group not having a (meth)acrylic group; (F) a low molecular weight compound having both a (meth)acrylic group and a hydroxy group; and (G) a crosslinking catalyst. (In the above formula, R １ represents a hydrogen atom or a methyl group, R ２ represents a linear or branched alkyl group having 1 to 5 carbon atoms.

2. The cured film-forming composition according to claim 1, 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 claim 1, wherein the photoalignable group of component (A) is a cinnamoyl group.

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

5. The cured film-forming composition according to claim 1, wherein the crosslinking agent (B) is a polymer obtained by polymerizing a monomer selected from N-hydroxymethyl(meth)acrylamide and N-alkoxymethyl(meth)acrylamide compounds.

6. A cured film obtained from the cured film-forming composition according to any one of claims 1 to 5.

7. An optical film having the cured film according to claim 6.

8. An alignment material formed using the cured film according to claim 6.

9. A retardation material formed using the cured film according to claim 6.

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