Cured film-forming composition, alignment material, and phase difference material

Abstract

The present invention addresses the problem of providing a cured film-forming composition for forming a cured film for forming an alignment material which has excellent solvent resistance, can align polymerizable liquid crystals with high sensitivity, and has little liquid crystal rejection. [Solution] A composition for forming a cured film, an alignment material, and a phase difference material. The composition for forming a cured film contains (A) a compound having a photo-alignment group, (B) a polymer having a structural unit having an N-hydroxymethyl group or an N-alkoxymethyl group, and (C) a cyclodextrin derivative in which some or all of hydroxyl groups are modified.

Description

TECHNICAL FIELD

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

[0002] In the case of a 3D display of a circularly polarized light glasses system, a retardation material is generally disposed on a display element such as a liquid crystal panel that forms an image. Two kinds of retardation regions having different phase difference characteristics are regularly disposed with a plurality of each, and a patterned retardation material is formed. Note that, hereinafter, in the present specification, such a patterned retardation material in which a plurality of retardation regions having different phase difference characteristics are disposed is referred to as a patterned retardation material.

[0003] A patterned retardation material can be produced by performing optical patterning on a retardation material formed of a polymerizable liquid crystal, as disclosed in, for example, Patent Literature 1. The optical patterning of a retardation material formed of a polymerizable liquid crystal utilizes a photo-alignment technique known in the formation of an alignment material for a liquid crystal panel. That is, a coating film formed of a photo-alignment material is provided on a substrate, and two kinds of polarized light having different polarized light directions are irradiated thereon. Further, a photo-alignment film is obtained as an alignment material that forms two kinds of liquid crystal alignment regions having different alignment control directions of liquid crystals. A solution-like retardation material including a polymerizable liquid crystal is coated on the photo-alignment film, and the alignment of the polymerizable liquid crystal is achieved. Then, the polymerizable liquid crystal that has been aligned is cured to form a patterned retardation material.

[0004] A reflection-preventing film of an organic EL display is composed of a linear polarizing plate and a 1 / 4 wavelength retardation plate, and extraneous light toward a panel surface of an image display panel is converted into linearly polarized light by the linear polarizing plate, and then converted into circularly polarized light by the 1 / 4 wavelength retardation plate. Here, the extraneous light based on the circularly polarized light is reflected on the surface of the image display panel or the like, but the direction of the plane of polarization is reversed at the time of the reflection. As a result, the reflected light is converted into linearly polarized light in a direction that is blocked by the linear polarizing plate by the 1 / 4 wavelength retardation plate after being opposite to the time of arrival, and then blocked by the linear polarizing plate, and as a result, the emission to the outside is significantly suppressed.

[0005] Regarding the 1 / 4 wavelength retardation plate, a method of composing the optical film by reverse dispersion characteristics by composing a 1 / 2 wavelength plate and a 1 / 4 wavelength plate is proposed in Patent Literature 2. In the case of this method, an optical film can be composed by reverse dispersion characteristics using a liquid crystal material based on positive dispersion characteristics in a wide wavelength band for the display of a color image.

[0006] Furthermore, in recent years, liquid crystal materials with anti-dispersion properties have been proposed as applicable to this phase retardation layer (Patent Documents 3 and 4). Based on such liquid crystal materials with anti-dispersion properties, instead of constructing a 1 / 4 wavelength phase retardation plate by combining two phase retardation layers of 1 / 2 wavelength plates and 1 / 4 wavelength plates, a single layer can be used to construct the phase retardation layer to ensure anti-dispersion properties. Thus, an optical film that can ensure the desired phase difference in a wide wavelength range can be realized with a simple structure.

[0007] Alignment layers are used to align liquid crystals. Methods for forming alignment layers include, for example, rubbing and photoalignment. Photoalignment is useful in terms of controlling the alignment process quantitatively, as it avoids the problems associated with rubbing.

[0008] For the formation of alignment materials using photo-alignment methods, acrylic resins and polyimide resins with photodimerization sites such as cinnamyl and chalcone groups in their side chains are known as materials with photo-alignment properties that can be utilized. The properties of these resins in controlling the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) by irradiation with polarized UV light have been reported (see Patent Documents 5 to 7).

[0009] In addition, there are examples of photoaligning agents using cinnamic yl groups that incorporate thermal crosslinking to improve orientation sensitivity and impart solvent resistance (see Patent Documents 8 and 9).

[0010] Existing technical documents

[0011] Patent documents

[0012] Patent Document 1: Japanese Patent Application Publication No. 2005-49865

[0013] Patent Document 2: Japanese Patent Application Publication No. 10-68816

[0014] Patent Document 3: US Patent No. 8,119,026

[0015] Patent Document 4: Japanese Patent Application Publication No. 2009-179563

[0016] Patent Document 5: Japanese Patent No. 3611342

[0017] Patent Document 6: Japanese Patent Application Publication No. 2009-058584

[0018] Patent Document 7: Japanese Patent Publication No. 2001-517719

[0019] Patent Document 8: International Patent Application Publication No. WO2011 / 126022

[0020] Patent Document 9: International Patent Application Publication No. WO2014 / 010688 Summary of the Invention

[0021] The problem that the invention aims to solve

[0022] In recent years, in order to reduce manufacturing costs, the production of optical materials using the optical alignment technology to manufacture phase difference materials has been required in addition to inexpensive resin films such as acrylic films, TAC (cellulose triacetate) films, and COP (cyclic olefin polymer) films. In particular, due to the excellent optical properties and reliability of acrylic films and the advantages of reducing manufacturing costs, there is a demand for the use of acrylic films as resin films (substrates).

[0023] However, for photoalignment films formed from existing materials as described above, due to the low solvent resistance of the alignment film, portions that repel liquid crystals are generated, i.e., so-called repulsion (…). This presents a problem of orientation defects.

[0024] This invention is based on the above findings and research results. Specifically, the object of this invention is to provide a composition for forming a cured film, wherein the cured film is used to form an alignment material with excellent solvent resistance, high sensitivity in aligning polymeric liquid crystals, and low repulsion.

[0025] In addition, the present invention aims to provide orientation materials and phase difference materials formed using the above-described cured film.

[0026] Other objects and advantages of the present invention will be apparent from the following description.

[0027] Methods for solving problems

[0028] In order to achieve the above-mentioned objectives, the inventors conducted in-depth research and found that by using cyclodextrin derivatives containing some or all of the modified hydroxyl groups, the rejection of liquid crystals can be suppressed, thereby completing the present invention with the following main objectives.

[0029] That is, the present invention includes the following.

[0030] [1] A composition for forming a cured film, comprising:

[0031] (A) Compounds with photooriented groups,

[0032] (B) Polymers having structural units having N-hydroxymethyl or N-alkoxymethyl groups, and

[0033] (C) Cyclodextrin derivatives with some or all of their hydroxyl groups modified.

[0034] [2] The composition for forming a cured film according to [1] above is characterized in that the photo-orientation group of component (A) is a functional group of a structure that undergoes photodimerization or photoisomerization.

[0035] [3] The composition for forming a cured film according to [1] above is characterized in that the photo-orientation group of component (A) is cinnamoyl.

[0036] [4] The composition for forming a cured film according to [1] above is characterized in that the photo-oriented group of component (A) is a group with an azobenzene structure.

[0037] [5] In the curing film forming composition described in [1] above, component (B) is a polymer that also has a structural unit having a partial structure as shown in formula (1).

[0038]

[0039] (In formula (1), Q1 represents an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or a phenyl group; Q2 represents O, S, or NQ3; Q3 is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms; and the dashed line represents a bonding bond.)

[0040] [6] The composition for forming a cured film according to [1] above is characterized in that it further contains a crosslinking catalyst as component (D).

[0041] [7] The composition for forming a cured film according to [1] above is characterized in that it further contains a bonding enhancement component as component (E).

[0042] [8] An oriented material, characterized in that it is obtained by using the curing film forming composition described in any one of [1] to [7] above.

[0043] [9] A phase difference material, characterized in that it is formed using a cured film obtained from any of the curing film forming compositions described in any one of [1] to [7] above.

[0044] The effects of the invention

[0045] According to the present invention, a composition for forming a curable film can be provided, wherein the curable film provides an alignment material having excellent solvent resistance, high sensitivity in aligning polymeric liquid crystals, and low repulsion of liquid crystals.

[0046] In addition, according to the present invention, an optical film having the above-described cured film, as well as an orientation material and a phase difference material formed using the cured film or the optical film, can be provided.

[0047] The mechanism by which the above-mentioned effects of the present invention are achieved may not be clear, but the following description is considered to be one reason.

[0048] (C) The cyclodextrin derivative of the component has high solvent resistance to liquid crystal solvents, thus it is easy to maintain the anisotropy of the orientation component and is not easy to generate dissolutions that become sources of repulsion. Furthermore, the leveling of the liquid crystal is improved by the surface hydrophilization brought about by the cyclodextrin. Detailed Implementation

[0049] The present invention will now be described in detail. It should be noted that the following description of the constituent elements is for illustrative purposes only, and the present invention is not limited to these descriptions.

[0050] <Composition for Curing Film Formation>

[0051] The curing film forming composition of the present invention comprises (A) a compound having a photooriented group, (B) a polymer having a structural unit having an N-hydroxymethyl or N-alkoxymethyl group and a structural unit having a partial structure shown in formula (1), and (C) a cyclodextrin derivative having some or all of its hydroxyl groups modified.

[0052] The following is a detailed explanation of each ingredient.

[0053] [(A)Component]

[0054] In the curing film forming composition of the present invention, component (A) is a compound having a photo-orientation group, and more specifically, a low-molecular-weight compound or polymer having both a photo-orientation group and a thermal crosslinking group. That is, component (A) is the component that imparts photoorientation to the cured film obtained from the curing film forming composition of the present invention, and in this specification, component (A) is also referred to as a photoorientation component.

[0055] <Low molecular weight compounds with photooriented and thermally crosslinked groups>

[0056] In the composition for forming a cured film according to the present invention, the low molecular weight compound of component (A) is a compound having a photooriented group, and may further be a compound having a group selected from hydroxyl, carboxyl, amide, amino and alkoxysilyl groups.

[0057] It should be noted that, in this invention, the term "photooriented group" generally refers to a functional group that exhibits the property of orientation upon light irradiation, and representatively refers to functional groups at structural sites undergoing photodimerization or photoisomerization. Other photooriented groups include, for example, functional groups that undergo photoFries rearrangement reactions (example compounds: benzoate ester compounds, etc.) and groups that undergo photodecomposition reactions (example compounds: cyclobutane rings, etc.).

[0058] The low-molecular-weight compound of component (A) can serve as a photo-oriented group and has a structural site for photodimerization, which is the site that forms a dimer through light irradiation. Specific examples include cinnamyl, chalcone, coumarin, and anthracene groups. Among these, cinnamyl is preferred considering its high transparency in the visible light region and its high photodimerization reactivity.

[0059] Furthermore, the so-called low-molecular-weight compounds of component (A) can have photoisomerization sites as photooriented groups, referring to structural sites that change between the cis and trans forms through light irradiation. Specific examples include structures composed of azobenzene... The structural components, etc. Among them, considering high reactivity, the azobenzene structure is preferred.

[0060] Low molecular weight compounds having a photooriented group and a group selected from hydroxyl, carboxyl, amide, amino, and alkoxysilyl groups are, for example, compounds shown in the following formula.

[0061]

[0062] In the above formula, A 1 and A 2 Each can be used independently to represent a hydrogen atom or a methyl group.

[0063] X 11 It is a structure formed by one to three substituents selected from alkylene, phenylene, biphenylene or combinations thereof having 1 to 18 carbon atoms, linked by one or more bonds selected from single bonds, ether bonds, ester bonds, amide bonds, urea bonds, urethane bonds, amino bonds, carbonyl bonds or combinations thereof, or it can be a structure formed by multiple links of the above substituents linked by each of the above bonds.

[0064] X 12 This refers to a hydrogen atom, a halogen atom, a cyano group, or an alkyl, phenyl, biphenyl, or cyclohexyl group having 1 to 18 carbon atoms. In this case, two or more groups of alkyl, phenyl, biphenyl, and cyclohexyl groups having 1 to 18 carbon atoms can be linked via single bonds, ether bonds, ester bonds, amide bonds, or urea bonds.

[0065] X 13 It represents hydroxyl, mercapto, alkoxy with 1 to 10 carbon atoms, alkylthio with 1 to 10 carbon atoms, phenoxy, biphenyloxy, or phenyl.

[0066] X 14 This indicates a single bond, an alkylene group with 1 to 20 carbon atoms, a divalent aromatic cyclic group, or a divalent aliphatic cyclic group. The alkylene group with 1 to 20 carbon atoms can be branched or linear.

[0067] X 15This indicates a hydroxyl, carboxyl, amide, amino, or alkoxysilyl group. Where X... 14 When it is a single bond, X 15 It can be hydroxyl or amino.

[0068] X represents a single bond, an oxygen atom, or a sulfur atom. Where X... 14 When X is a single bond, it is also a single bond.

[0069] It should be noted that when these substituents include a benzene ring, the hydrogen atom on the benzene ring can be replaced by one or more of the same or different substituents selected from alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, trifluoromethyl groups, and cyano groups.

[0070] In the above formula, R 11 R 12 R 13 R 14 R 15 R 16 R 17 and R 18 Each can independently represent 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.

[0071] Specific examples of low-molecular-weight compounds having photooriented groups and hydroxyl groups as component (A) include, for example, compounds shown in formulas [A11] to [A15] above, and compounds other than those formulas, such as methyl 4-(8-hydroxyoctyloxy)cinnamate, methyl 4-(6-hydroxyhexyloxy)cinnamate, methyl 4-(4-hydroxybutyloxy)cinnamate, methyl 4-(3-hydroxypropyloxy)cinnamate, methyl 4-(2-hydroxyethyloxy)cinnamate, methyl 4-hydroxymethyloxy)cinnamate, methyl 4-hydroxycinnamate, ethyl 4-(8-hydroxyoctyloxy)cinnamate, ethyl 4-(6-hydroxyhexyloxy)cinnamate, ethyl 4-(4-hydroxybutyloxy)cinnamate, ethyl ...ethyloxy)cinnamate, ethyl 4-(8-hydroxyoctyloxy)cinnamate, ethyl 4-(6-hydroxyhexyloxy)cinnamate, ethyl 4-(4-hydroxybutyloxy)cinnamate, ethyl 4-(8-hydroxyoctyloxy)cinnamate, ethyl 4-(6-hydroxyhexyloxy)cinnamate, ethyl 4-(4-hydroxybutyloxy)cinnamate, ethyl 4-(8-hydroxyoctyloxy)cinnamate, ethyl 4-(6-hydroxyhexyloxy)cinnamate, ethyl 4-(4-hydroxybutyloxy)cinnamate, ethyl 4-(8-hydroxyoctyloxy) Ethyl 4-(2-hydroxyethyloxy)cinnamate, ethyl 4-hydroxymethyloxy)cinnamate, ethyl 4-hydroxycinnamate, ethyl 4-hydroxycinnamate, phenyl 4-(8-hydroxyoctyloxy)cinnamate, phenyl 4-(6-hydroxyhexyloxy)cinnamate, phenyl 4-(4-hydroxybutyloxy)cinnamate, phenyl 4-(3-hydroxypropyloxy)cinnamate, phenyl 4-(2-hydroxyethyloxy)cinnamate, phenyl 4-hydroxymethyloxy)cinnamate, phenyl 4-hydroxycinnamate, biphenyl 4-(8-hydroxyoctyloxy)cinnamate, biphenyl 4-(6-hydroxyhexyloxy)cinnamate, biphenyl 4-(4-hydroxybutyloxy)cinnamate, biphenyl 4-(3-hydroxypropyloxy)cinnamate, biphenyl 4-(6-hydroxyhexyloxy)cinnamate, biphenyl 4-(4-hydroxybutyloxy)cinnamate, biphenyl 4-(3-hydroxypropyloxy)cinnamate, biphenyl 4-(2- Biphenyl cinnamate (hydroxyethyloxy) , 4-hydroxymethyloxybiphenyl cinnamate, 4-hydroxycinnamate, 8-hydroxyoctyl cinnamate, 6-hydroxyhexyl cinnamate, 4-hydroxybutyl cinnamate, 3-hydroxypropyl cinnamate, 2-hydroxyethyl cinnamate, hydroxymethyl cinnamate, 4-(8-hydroxyoctyloxy)azobenzene, 4-(6-hydroxyhexyloxy)azobenzene, 4-(4-hydroxybutyloxy)azobenzene, 4-(3-hydroxypropyloxy)azobenzene, 4-(2-hydroxyethyloxy)azobenzene, 4-hydroxymethyloxyazobenzene, 4-hydroxyazobenzene, 4-(8-hydroxyoctyloxy)chalcone, 4-(6-hydroxyhexyloxy)chalcone, 4-(4-hydroxybutyloxy)chalcone, 4- (3-Hydroxypropyloxy)chalcone, 4-(2-Hydroxyethyloxy)chalcone, 4-Hydroxymethyloxychalcone, 4-Hydroxychalcone, 4'-(8-Hydroxyoctyloxy)chalcone, 4'-(6-Hydroxyhexyloxy)chalcone, 4'-(4-Hydroxybutyloxy)chalcone, 4'-(3-Hydroxypropyloxy)chalcone, 4'-(2-Hydroxyethyloxy)chalcone, 4'-Hydroxymethyloxychalcone, 4'-Hydroxychalcone, 7-(8-Hydroxyoctyloxy)coumarin, 7-(6-Hydroxyhexyloxy)coumarin, 7-(4-Hydroxybutyloxy)coumarin, 7-(3-Hydroxypropyloxy)coumarin, 7-(2-Hydroxyethyloxy)coumarin, 7-Hydroxymethyloxycoumarin7-Hydroxycoumarin, 6-(8-Hydroxyoctyloxy)coumarin, 6-(6-Hydroxyhexyloxy)coumarin, 6-(4-Hydroxybutyloxy)coumarin, 6-(3-Hydroxypropyloxy)coumarin, 6-(2-Hydroxyethyloxy)coumarin, 6-Hydroxymethyloxycoumarin, 6-Hydroxycoumarin, methyl 4-[4-(8-Hydroxyoctyloxy)benzoyl]cinnamate, methyl 4-[4-(6-Hydroxyhexyloxy)benzoyl]cinnamate, methyl 4-[4-(4-Hydroxybutyloxy)benzoyl]cinnamate, methyl 4-[4-(3-Hydroxypropyloxy)benzoyl]cinnamate, methyl 4-[4-(2-Hydroxyethyloxy)benzoyl]cinnamate, methyl 4-[4-Hydroxymethyloxybenzoyl] Methyl cinnamate, 4-[4-hydroxybenzoyl]methyl cinnamate, 4-[4-(8-hydroxyoctyloxy)benzoyl]ethyl cinnamate, 4-[4-(6-hydroxyhexyloxy)benzoyl]ethyl cinnamate, 4-[4-(4-hydroxybutyloxy)benzoyl]ethyl cinnamate, 4-[4-(3-hydroxypropyloxy)benzoyl]ethyl cinnamate, 4-[4-(2-hydroxyethyloxy)benzoyl]ethyl cinnamate, 4-[4-hydroxymethyloxybenzoyl]ethyl cinnamate, 4-[4-hydroxybenzoyl]ethyl cinnamate, 4-[4-hydroxybenzoyl]tert-butyl cinnamate, 4-[4-(8-hydroxyoctyloxy)benzoyl]tert-butyl cinnamate, 4-[4-(6-hydroxyhexyloxy)benzoyl]tert-butyl cinnamate, 4-[4-(4-hydroxybutyl ... [4-[4-(3-hydroxypropyloxy)benzoyl] tert-butyl cinnamate, [4-[4-(2-hydroxyethyloxy)benzoyl] tert-butyl cinnamate, [4-[4-hydroxymethyloxybenzoyl] tert-butyl cinnamate, [4-[4-(8-hydroxyoctyloxy)benzoyl] phenyl cinnamate, [4-[4-(6-hydroxyhexyloxy)benzoyl] phenyl cinnamate, [4-[4-(4-hydroxybutyloxy)benzoyl] phenyl cinnamate, [4-[4-(3-hydroxypropyloxy)benzoyl] phenyl cinnamate, [4-[4-(2-hydroxyethyloxy)benzoyl] phenyl cinnamate, [4-[4-hydroxymethyloxybenzoyl] phenyl cinnamate, [4-[4-hydroxybenzoyl] cinnamate] phenyl cinnamate, [4-[4-hydroxymethyloxybenzoyl] phenyl cinnamate, [4-[4-hydroxybenzoyl] cinnamate] phenyl cinnamate, [4-[4-hydroxybenzoyl] cinnamate] phenyl cinnamate, [4-[4-hydroxybenzoyl] cinnamate] phenyl cinnamate, [4-[4-hydroxybenzoyl] cinnamate] phenyl cinnamate, [4-[4-hydroxybenzoyl] cinnamate] phenyl cinnamate, [4-[4-hydroxybenzoyl] cinnamate] phenyl cinnamate, [4-[4-hydroxybenzoyl] cinnamate] phenyl cinnamate, [4-[4-hydroxybenzoyl] cinnamate] phenyl cinnamate, [4-hydroxybenzoyl] cinnamate Biphenyl cinnamate, 4-[4-(8-hydroxyoctyloxy)benzoyl] cinnamate, 4-[4-(6-hydroxyhexyloxy)benzoyl] cinnamate, 4-[4-(4-hydroxybutyloxy)benzoyl] cinnamate, 4-[4-(3-hydroxypropyloxy)benzoyl] cinnamate, 4-[4-(2-hydroxyethyloxy)benzoyl] cinnamate, 4-[4-hydroxymethyloxybenzoyl] cinnamate, 4-[4-hydroxybenzoyl] cinnamate, 4-benzoylcinnamate 8-hydroxyoctyl ester, 4-benzoylcinnamate 6-hydroxyhexyl ester, 4-benzoylcinnamate 4-hydroxybutyl ester, 4-benzoylcinnamate 3-hydroxypropyl ester, 4-benzoylcinnamate 2-hydroxyethyl ester4-Benzoylcinnamate hydroxymethyl ester, 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 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, etc.

[0072] Specific examples of low molecular weight compounds having photo-oriented groups and carboxyl groups as component (A) include cinnamic acid, ferulic acid, 4-methoxycinnamic acid, 4-propoxycinnamic acid, 3,4-dimethoxycinnamic acid, coumarin-3-carboxylic acid, 4-(N,N-dimethylamino)cinnamic acid, etc.

[0073] Specific examples of low molecular weight compounds having photo-oriented groups and amide groups as component (A) include cinnamic acid amide, 4-methylcinnamic acid amide, 4-ethylcinnamic acid amide, 4-methoxycinnamic acid amide, 4-ethoxycinnamic acid amide, etc.

[0074] Specific examples of low molecular weight compounds having a photooriented group and an amino group as component (A) include methyl 4-aminocinnamate, ethyl 4-aminocinnamate, methyl 3-aminocinnamate, ethyl 3-aminocinnamate, etc.

[0075] Specific examples of low molecular weight compounds having a photooriented group and an alkoxysilyl group as component (A) include methyl 4-(3-trimethoxysilylpropyloxy)cinnamate, methyl 4-(3-triethoxysilylpropyloxy)cinnamate, ethyl 4-(3-trimethoxysilylpropyloxy)cinnamate, ethyl 4-(3-triethoxysilylpropyloxy)cinnamate, methyl 4-(3-trimethoxysilylhexyloxy)cinnamate, methyl 4-(3-triethoxysilylhexyloxy)cinnamate, ethyl 4-(3-trimethoxysilylhexyloxy)cinnamate, and ethyl 4-(3-triethoxysilylhexyloxy)cinnamate.

[0076] The low molecular weight compound that is component (A) is preferably a compound obtained by combining a polymerizable group with a group consisting of a photooriented site and a thermally reactive site as shown in formula (a-1) via a spacer group.

[0077]

[0078] (where R is in the formula) 101 X represents hydroxyl, amino, hydroxyphenoxy, carboxyphenoxy, aminophenoxy, aminocarbonylphenoxy, phenylamino, hydroxyphenylamino, carboxyphenylamino, aminophenylamino, hydroxyalkylamino, or bis(hydroxyalkyl)amino. 101 This indicates a phenylene group that can be substituted by any substituent, where the hydrogen atom on the benzene ring can be replaced by the substituent.

[0079] Examples of substituents that can replace hydrogen atoms on the benzene ring include alkyl groups such as methyl, ethyl, propyl, butyl, and isobutyl; haloalkyl groups such as trifluoromethyl; alkoxy groups such as methoxy and ethoxy; halogen atoms such as iodine, bromine, chlorine, and fluorine; cyano; and nitro.

[0080] The above R 101 In this mixture, hydroxyl and amino groups are preferred, with hydroxyl groups being particularly preferred.

[0081] The spacer group is a divalent group selected from linear alkylene, branched alkylene, cyclic alkylene, and phenylene, or represents a group formed by the combination of multiple such divalent groups. In this case, the bonds between the divalent groups constituting the spacer group, the bonds between the spacer group and the group shown in formula (a-1) above, and the bonds between the spacer group and the polymerizable group can be single bonds, ester bonds, amide bonds, urea bonds, or ether bonds. When there are multiple divalent groups, the divalent groups can be the same or different from each other; when there are multiple bonds, the bonds can be the same or different from each other.

[0082] Examples of low-molecular-weight compounds in which the polymerizable group of component (A) is combined with a group formed by the combination of a photooriented site and a thermally reactive site include 4-(6-methacryloyloxyhexyl-1-oxy)cinnamic acid, 4-(6-acryloyloxyhexyl-1-oxy)cinnamic acid, 4-(3-methacryloyloxypropyl-1-oxy)cinnamic acid, 4-(4-(3-methacryloyloxypropyl-1-oxy)acryloyloxy)benzoic acid, 4-(4-(6-methacryloyloxyhexyl-1-oxy)benzoyloxy)cinnamic acid, 4-(6-methacryloyloxyhexyl-1-oxy)cinnamicamide, 4-(6-methacryloyloxyhexyl-1-oxy)-N-(4-cyanophenyl)cinnamicamide, and 4-(6-methacryloyloxyhexyl-1-oxy)-N-dihydroxyethylcinnamicamide.

[0083] The above are specific examples of low molecular weight photoorientation components that are components of (A), but are not limited to these.

[0084] As described above, in this invention, low molecular weight compounds can be used as component (A). Furthermore, component (A) can also be a mixture of one or more low molecular weight compounds.

[0085] <Polymers with photooriented and thermally crosslinked groups>

[0086] In the curable film forming composition of the present invention, the polymer of component (A) is preferably a polymer having a photo-oriented group, that is, a polymer having a functional group of a structural site for photodimerization or photoisomerization as a photo-oriented group, particularly an acrylic copolymer having at least a photodimerization site. Furthermore, it is desirable for an acrylic copolymer to have, in addition to the photodimerization site, a group selected from hydroxyl, carboxyl, amide, amino, and alkoxysilyl groups (hereinafter, including these groups, also referred to as a thermal crosslinking site).

[0087] In this invention, the term "acrylic copolymer" refers to a copolymer obtained by polymerizing monomers such as acrylates, methacrylates, and styrene that have unsaturated double bonds.

[0088] (A) An acrylic copolymer with photodimerization site and thermal crosslinking site (hereinafter also referred to as a specific copolymer). Any acrylic copolymer with such a structure is acceptable, and there are no particular restrictions on the backbone and side chain types of the polymer main chain constituting the acrylic copolymer.

[0089] Examples of photodimerization sites include cinnamyl, chalcone, coumarin, and anthracene. Among these, cinnamyl is preferred due to its high transparency in the visible light region and high photodimerization reactivity. More preferred cinnamyl groups and substituents containing the cinnamyl structure include structures shown in formula [1] or [2]. It should be noted that in this specification, the term "cinnamyl group" and "substituents containing the cinnamyl structure" also include groups with a naphthalene ring in the cinnamyl group.

[0090]

[0091] In the above formula [1], X 1 This refers to an alkyl, phenyl, or biphenyl group containing 1 to 18 carbon atoms, with hydrogen atoms. In this case, the hydrogen atoms on the phenyl and biphenyl groups can be replaced by any of the halogen atoms and cyano groups.

[0092] In the above formula [2], X 2This refers to a hydrogen atom, a cyano group, and an alkyl, phenyl, biphenyl, or cyclohexyl group having 1 to 18 carbon atoms. In this case, multiple alkyl, phenyl, biphenyl, or cyclohexyl groups having 1 to 18 carbon atoms can be bonded via one or more bonds selected from single bonds, ether bonds, ester bonds, amide bonds, urea bonds, carbamate bonds, amino bonds, carbonyl bonds, or combinations thereof.

[0093] In the above formulas [1] and [2], A represents any one of formulas [A1], [A2], [A3], [A4], [A5] and [A6].

[0094] In the above equations [A1], [A2], [A3], [A4], [A5], and [A6], R 31 R 32 R 33 R 34 R 35 R 36 R 37 and R 38 Each can independently represent 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.

[0095] The thermal cross-linking site is the site that combines with the cross-linking agent, which is component (B), through heating. Specific examples include hydroxyl, carboxyl, amide, amino, alkoxysilyl, etc.

[0096] (A) The acrylic copolymer of component A is preferably of weight average molecular weight of 3,000 to 200,000. If the weight average molecular weight exceeds 200,000 and is too large, the solubility in solvents may decrease and the workability may decrease. On the other hand, if the weight average molecular weight is less than 3,000 and is too small, it may become insufficiently cured during thermosetting and the solvent resistance or heat resistance may decrease.

[0097] Regarding the synthesis method of acrylic copolymers with photodimerization sites and thermal crosslinking sites of component (A), the method of copolymerizing monomers with photodimerization sites and monomers with thermal crosslinking sites is simple.

[0098] Examples of monomers having a photodimerization site include monomers having cinnamyl, chalcone, coumarin, anthracene, etc. Among these, monomers having a cinnamyl group are particularly preferred considering their high transparency in the visible light region and high photodimerization reactivity.

[0099] More preferably, monomers having a cinnamoyl group having the structure shown in formula [1] or formula [2] and monomers containing substituents of the cinnamoyl group structure are preferred. Specific examples of such monomers are those shown in formula [3] or formula [4].

[0100]

[0101] In the above formula [3], X 1 This refers to an alkyl, phenyl, or biphenyl group containing 1 to 18 carbon atoms, with hydrogen atoms. In this case, the hydrogen atoms on the phenyl and biphenyl groups can be replaced by any of the halogen atoms and cyano groups.

[0102] L 1 and L 2 Each can be represented independently as a single bond, ether bond, ester bond, amide bond, urea bond, or carbamate bond.

[0103] In the above formula [4], X 2 This refers to a hydrogen atom, a cyano group, and an alkyl, phenyl, biphenyl, or cyclohexyl group having 1 to 18 carbon atoms. In this case, multiple alkyl, phenyl, biphenyl, or cyclohexyl groups having 1 to 18 carbon atoms can be bonded via one or more bonds selected from single bonds, ether bonds, ester bonds, amide bonds, urea bonds, carbamate bonds, amino bonds, carbonyl bonds, or combinations thereof.

[0104] In equations [3] and [4] above, X 3 and X 5 Each can independently represent a single bond, an alkylene ring with 1 to 20 carbon atoms, a divalent aromatic ring, or a divalent aliphatic ring. Here, the alkylene ring with 1 to 20 carbon atoms can be branched or straight-chain.

[0105] In equations [3] and [4] above, X 4 This indicates a polymerizable group. Specific examples of such polymerizable groups include, for instance, acryloyl, methacryloyl, styrene, maleimide, acrylamide, and methacrylamide.

[0106] In the above equations [3] and [4], A represents any one of equations [A1], [A2], [A3], [A4], [A5] and [A6] in the same way as above.

[0107] Examples of monomers with thermally crosslinked sites include, for example, 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 acrylate, caprolactone 2-(methacryloyloxy)ethyl acrylate, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornen-2-carboxy-6-lactone, 5-methacryloyloxy-6-hydroxynorbornen-2-carboxy-6-lactone, etc., monomers with hydroxyl groups; acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phenyl diacrylate, etc. Monomers containing carboxyl groups, such as formate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide; monomers containing phenolic hydroxyl groups, such as hydroxystyrene, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)maleimide, and N-(hydroxyphenyl)maleimide; monomers containing amide groups, such as acrylamide and methacrylamide; monomers containing alkoxysilyl groups, such as methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, acryloyloxypropyltrimethoxysilane, and acryloyloxypropyltriethoxysilane; and monomers containing amino groups, such as dimethylaminoethyl methacrylate, diethylamino methacrylate, and tert-butylaminoethyl methacrylate.

[0108] The amounts of monomers with photodimerization sites and monomers with thermal crosslinking sites used to obtain a specific copolymer are preferably based on the total amount of all monomers used to obtain the specific copolymer, with the amount of monomers with photodimerization sites being 40% to 95% by mass and the amount of monomers with thermal crosslinking sites being 5% to 60% by mass. By making the content of monomers with photodimerization sites 40% by mass or more, high sensitivity and good liquid crystal alignment can be imparted. On the other hand, by making it 95% by mass or less, sufficient thermosetting properties can be imparted, and high sensitivity and good liquid crystal alignment can be maintained.

[0109] Furthermore, in the curing film forming composition of the present invention, when obtaining a specific copolymer, it is possible to use monomers (hereinafter also referred to as monomers having non-reactive functional groups) that are capable of copolymerizing with monomers having photodimerization sites and thermal crosslinking sites (hereinafter also referred to as specific functional groups).

[0110] Specific examples of such monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

[0111] The following are specific examples of the aforementioned monomers, but the present invention is not limited to these.

[0112] Examples of the aforementioned acrylate compounds include, for instance, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracene methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

[0113] Examples of the aforementioned methacrylate compounds include, for instance, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracene methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

[0114] Examples of the aforementioned vinyl compounds include, for example, methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-vinyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

[0115] Examples of the aforementioned styrene compounds include styrene, methylstyrene, chlorostyrene, and bromostyrene.

[0116] Examples of the aforementioned maleimide compounds include, for example, maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0117] The method for obtaining the specific copolymer used in the curable film forming composition of the present invention is not particularly limited. Examples include a method in which a polymerization reaction is carried out at a temperature of 50°C to 110°C in a solvent in which monomers having specific functional groups (monomers having photodimerization sites and monomers having thermal crosslinking sites), monomers having non-reactive functional groups as needed, and a polymerization initiator coexist. In this case, the solvent used is not particularly limited as long as it can dissolve the monomers having specific functional groups, the monomers having non-reactive functional groups used as needed, and the polymerization initiator. As specific examples, solvents described below can be cited.

[0118] The specific copolymer obtained by this operation is usually in the state of a solution dissolved in a solvent, and in this invention it can be used directly in the form of a polymer solution of component (A).

[0119] Furthermore, by adding a solution of the specific copolymer obtained as described above to ether, water, or similar solvent and stirring to allow it to redefine, and then filtering / washing the resulting precipitate, followed by drying at room temperature or with heat under normal or reduced pressure, a powder of the specific copolymer can be produced. This process removes polymerization initiators and unreacted monomers that coexist with the specific copolymer, resulting in a refined powder of the specific copolymer. If sufficient purification cannot be achieved in a single operation, the above process can be repeated by dissolving the obtained powder in a solvent.

[0120] In the curing film forming composition of the present invention, the powder of the above-mentioned specific copolymer can be used directly as the polymer of component (A), or the powder can be dissolved in a solvent such as those described later and used in a solution state.

[0121] In addition, the polymer used as component (A) can also be a polymer obtained by reacting a cinnamic acid derivative with a polymer having epoxy groups on the side chain.

[0122] Polymers with epoxy groups on their side chains can be, for example, polymers of polymeric unsaturated compounds with epoxy groups or copolymers of polymeric unsaturated compounds with epoxy groups and other polymeric unsaturated compounds.

[0123] Specific examples of polymerizable unsaturated compounds having epoxy groups include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc.

[0124] Other polymerizable unsaturated compounds include alkyl (meth)acrylates, cyclic (meth)acrylates, aryl methacrylates, aryl acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other polymerizable unsaturated compounds.

[0125] Specific examples of these include, as alkyl methacrylates, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloyloxyethyl glycoside, 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, and n-stearyl methacrylate; as alkyl acrylates, methyl acrylate and isopropyl acrylate are examples; and as cyclic alkyl methacrylates, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, and tricyclic [5.2.1.0] are examples. 2,6 [Decane-8-ylmethacrylate, tricyclic [5.2.1.0]] 2,6 Decane-8-yloxyethyl methacrylate, isobornyl methacrylate, cholesteryl methacrylate, etc.; as cyclic alkyl acrylates, examples include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0] 2,6 [Decane-8-yl acrylate, tricyclic [5.2.1.0]] 2,6Decane-8-yloxyethyl acrylate, isobornyl acrylate, cholesteryl acrylate, etc.; as aryl methacrylates, examples include phenyl methacrylate, benzyl methacrylate, etc.; as aryl acrylates, examples include phenyl acrylate, benzyl acrylate, etc.; as unsaturated dicarboxylic acid diesters, examples include diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc.

[0126] Examples of dicyclic unsaturated compounds include, for instance, bicyclic [2.2.1]hept-2-ene, 5-methylbicyclic [2.2.1]hept-2-ene, 5-ethylbicyclic [2.2.1]hept-2-ene, 5-methoxybicyclic [2.2.1]hept-2-ene, 5-ethoxybicyclic [2.2.1]hept-2-ene, 5,6-dimethoxybicyclic [2.2.1]hept-2-ene, 5,6-diethoxybicyclic [2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclic [2.2.1]hept-2-ene, 5, Examples of maleimide compounds include 6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, and 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene; Examples of maleimide compounds include N-phenylmaleimide and N-cyclohexylmaleimide. Imines, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6-maleimide hexanoate, N-succinimide-3-maleimide propionate, N-(9-acridyl)maleimide, etc.; as unsaturated aromatic compounds, examples include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, etc.; as conjugated diene compounds, examples include 1 Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, and crotonic acid; examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, succinic acid, and itaconic acid; examples of unsaturated dicarboxylic acid anhydrides include the anhydrides of the aforementioned unsaturated dicarboxylic acids; and examples of polymerizable unsaturated compounds other than those mentioned above include acrylonitrile, methacrylonitrile, vinyl chloride, 1,1-dichloroethylene, acrylamide, methacrylamide, and vinyl acetate.

[0127] The copolymerization ratio of the epoxy-containing polymeric unsaturated compound in the polymer having epoxy groups in the side chain is preferably 30% by mass or more, more preferably 50% by mass or more.

[0128] The synthesis of polymers with epoxy groups on the side chains can preferably be carried out by known free radical polymerization in the presence of a suitable polymerization initiator in a solvent.

[0129] Commercially available products can also be used as polymers with epoxy groups on the side chains. Examples of such commercially available products include EHPE3150 and EHPE3150CE (and above). (manufactured), UG-4010, UG-4035, UG-4040, UG-4070 (and above, manufactured by Toa Gosei Co., Ltd. ARUFON series), ECN-1299 (manufactured by Asahi Kasei Co., Ltd.), DEN431, DEN438 (and above, (Company), jER-152 ( (manufactured by) (Company) N-660, N-665, N-670, N-673, N-695, N-740, N-770, N-775 (and above, DIC (sole propagation)) (manufactured by Nippon Kayaku Co., Ltd.), EOCN-1020, EOCN-102S, EOCN-104S (above, manufactured by Nippon Kayaku Co., Ltd.), etc.

[0130] Examples of cinnamic acid derivatives include cinnamic acid derivatives having a carboxyl group, and examples include compounds represented by any of the formulas (1-1) to (1-5) below.

[0131]

[0132] (In the formula, R1 represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, etc.)

[0133] Furthermore, as a cinnamic acid derivative with a carboxyl group, it is also suitable for use in the monomer shown in the above formula [3], X 1 Compounds containing hydrogen atoms.

[0134] The compounds shown in formulas (1-1) to (1-5) above can be synthesized by appropriately combining conventional organic chemistry methods.

[0135] The reaction products of the polymers with epoxy groups on the side chains and cinnamic acid derivatives described above can be synthesized by reacting the polymers with epoxy groups as described above with cinnamic acid derivatives, preferably in the presence of a catalyst and preferably in a suitable organic solvent.

[0136] The proportion of cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 moles relative to 1 mole of epoxy group contained in the epoxy-containing polymer, more preferably 0.05 to 1.3 moles, and even more preferably 0.1 to 1.1 moles.

[0137] As a catalyst that can be used here, an organic base or a known compound that is a so-called curing accelerator that promotes the reaction of epoxy compounds with acid anhydrides can be used.

[0138] Examples of such organic bases include primary or secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and diazabicycloundecene; and quaternary organic amines such as tetramethylammonium hydroxide. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, pyridine, and 4-dimethylaminopyridine, and quaternary organic amines such as tetramethylammonium hydroxide are preferred.

[0139] Examples of curing accelerators include tertiary amines such as benzyl dimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyl dimethylamine, and triethanolamine; 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-(2-cyanoethyl)-2 1-Methylimidazole, 1-(2-cyanoethyl)-2-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2-phenyl-4,5-di[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-undecylimidazole Trimethicone, 1-(2-cyanoethyl)-2-phenylimidazolium Trimethicone salt, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium Trimethicone salts, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyltriazine, 2,4-diamino-6-(2'-n-undecylimidazolyl)ethyltriazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyltriazine, isocyanuric acid adducts of 2-methylimidazolium, isocyanuric acid adducts of 2-phenylimidazolium, imidazole compounds such as isocyanuric acid adducts of 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyltriazine; organophosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenyl phosphite;

[0140] such as benzyltriphenylchloride tetra-n-butyl bromide Methyltriphenylbromide ethyltriphenylbromide n-Butyltriphenylbromide Tetraphenylbromide ethyltriphenyliodide ethyltriphenyl Acetate, tetra-n-butyl o,o-diethyldithiophosphate, tetra-n-butyl benzotriazole salt, tetra-n-butyl Tetrafluoroborate, tetra-n-butyl Tetraphenylborate, tetraphenyl Tetraphenylborate, like quaternary Salts; such as 1,8-diazabicyclo[5.4.0]undecene-7 and its organic acid salts, such as diazabicycloolefins; such as zinc 2-ethylhexanoate, tin 2-ethylhexanoate, and aluminum acetylacetone coordination compounds; such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride, such as quaternary ammonium salts; such as boron trifluoride and triphenyl borate; such as zinc chloride and tin chloride, such as metal halide compounds; high-melting-point dispersible latent curing accelerators such as dicyandiamide, amine-epoxy resin adducts, etc.; imidazole compounds, organophosphorus compounds, and quaternary ammonium salts. Microencapsulated latent curing accelerators with polymer coatings on the surface of curing accelerators such as salts; amine salt type latent curing accelerators; latent curing accelerators such as Lewis acid salts and Brønsted salts that undergo high-temperature dissociation and thermal cationic polymerization, etc.

[0141] Among them, benzyltriphenylchloride is preferred. tetra-n-butyl bromide Methyltriphenylbromide ethyltriphenylbromide n-Butyltriphenylbromide Tetraphenylbromide ethyltriphenyliodide ethyltriphenyl Acetate, tetra-n-butyl o,o-diethyldithiophosphate, tetra-n-butyl benzotriazole salt, tetra-n-butyl Tetrafluoroborate, tetra-n-butyl Tetraphenylborate, tetraphenyl Tetraphenylborate, like quaternary Salts; such as quaternary ammonium salts like tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.

[0142] The proportion of the catalyst used is preferably less than 100 parts by mass relative to 100 parts by mass of the polymer having epoxy groups, more preferably 0.01 to 100 parts by mass, and even more preferably 0.1 to 20 parts by mass.

[0143] Examples of organic solvents include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, and alcohol compounds. Among these, ether compounds, ester compounds, ketone compounds, and alcohol compounds are preferred from the viewpoint of the solubility of the raw materials and products, as well as the ease of purification of the products. The solvent is used in an amount preferably 0.1% by mass or more, more preferably 5 to 50% by mass, of solid content (the proportion of the mass of the components other than the solvent in the reaction solution to the total mass of the solution).

[0144] The reaction temperature is preferably 0–200°C, more preferably 50–150°C. The reaction time is preferably 0.1–50 hours, more preferably 0.5–20 hours.

[0145] This process yields a solution containing the reaction product of an epoxy-based polymer and a cinnamic acid derivative. This solution can be used directly for the preparation of compositions for curing films, or it can be used after separating the polymer contained in the solution, or the separated polymer can be purified before being used for the preparation of compositions for curing films.

[0146] Furthermore, in this embodiment, the acrylic copolymer of component (A) may also be a mixture of various specific copolymers.

[0147] As described above, in this invention, a high molecular weight specific copolymer can be used as component (A). Furthermore, component (A) can also be a mixture of one or more specific copolymers.

[0148] [(B) Component]

[0149] The (B) component contained in the curing film forming composition of the present invention is a polymer having a structural unit containing N-hydroxymethyl or N-alkoxymethyl, and more specifically, a polymer polymerized with a monomer having N-alkoxymethyl or N-hydroxymethyl (hereinafter also referred to as specific polymer 2).

[0150] As a monomer having N-alkoxymethyl or N-hydroxymethyl, compounds such as those shown in formula (X1) below are preferred.

[0151]

[0152] (where R is in the formula) 31 R represents a hydrogen atom or a methyl group. 32(representing hydrogen atoms, or alkyl groups with 1 to 10 carbon atoms in a straight or branched chain)

[0153] Specific examples of the compounds shown in formula (X1) above include N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, and other acrylamide compounds or methacrylamide compounds in which hydroxymethyl or alkoxymethyl groups have been substituted. It should be noted that (meth)acrylamide refers to both methacrylamide and acrylamide.

[0154] The specific polymer 2, which is component (B), can also be a copolymer of monomers having groups shown in the above formula (1) in addition to monomers having N-alkoxymethyl or N-hydroxymethyl groups.

[0155] In the above formula (1), the alkyl group with 1 to 6 carbon atoms represented by Q1 is preferably an alkyl group with 1 to 5 carbon atoms.

[0156] Examples of such alkyl groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1 , 1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, etc.

[0157] Among them, methyl, ethyl, n-propyl, n-butyl and isobutyl are preferred.

[0158] In the above formula (1), the alkoxy group with 1 to 6 carbon atoms represented by Q1 is preferably an alkoxy group with 1 to 5 carbon atoms.

[0159] Examples of such alkoxy groups include, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexoxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy. Oxygen compounds, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2,-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy, etc.

[0160] Among them, methoxy, ethoxy and n-propoxy are preferred.

[0161] In formula (1) above, Q2 represents O, S or NQ3, and Q3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms represented by Q3 can be given in the specific examples of alkyl groups having 1 to 6 carbon atoms represented by Q1 above, with alkyl groups having 1 to 3 carbon atoms being preferred, and methyl groups being more preferred.

[0162] Examples of monomers having the group shown in formula (1) include acetoacetoxyethyl acrylate and acetoacetoxyethyl methacrylate.

[0163] The amount of N-hydroxymethyl or N-alkoxymethyl monomers used to obtain a polymer having an N-hydroxymethyl or N-alkoxymethyl structural unit is, based on the total amount of all monomers used to obtain the specific polymer 2, preferably 10 mol% to 100 mol%, more preferably 30 mol% to 100 mol%, and even more preferably 50 mol% to 100 mol%.

[0164] (B) When the component is a polymer having a structural unit having an N-hydroxymethyl or N-alkoxymethyl structure and a structural unit having a partial structure as shown in formula (1) above, the amount of monomers having an N-hydroxymethyl or N-alkoxymethyl structure and monomers having the group shown in formula (1) used to obtain the polymer is based on the total amount of all monomers used to obtain the specific polymer 2. The monomers having an N-hydroxymethyl or N-alkoxymethyl structure are preferably 10 mol% to 99.9 mol%, more preferably 30 mol% to 99 mol%, and even more preferably 50 mol% to 95 mol%. The monomers having the group shown in formula (1) are preferably 0.1 mol% to 90 mol%, more preferably 1 mol% to 70 mol%, and even more preferably 5 mol% to 50 mol%.

[0165] When obtaining a polymer having a structural unit having an N-hydroxymethyl or N-alkoxymethyl group and a structural unit according to the desired formula (1) above, a monomer having a non-reactive functional group, as exemplified in item (A) above, may be used. The amount of monomer having a non-reactive functional group used is the remainder if the total amount of the monomer having an N-hydroxymethyl or N-alkoxymethyl group and the monomer having the group shown in formula (1) is less than 100 mol%.

[0166] The weight-average molecular weight of such polymer as component (B) is preferably 1,000 to 500,000, more preferably 2,000 to 200,000, even more preferably 3,000 to 150,000, and particularly preferably 3,000 to 50,000.

[0167] These polymers, which are components (B), can be used alone or in combination of two or more.

[0168] The content of the polymer having a structural unit having an N-hydroxymethyl or N-alkoxymethyl structure and a structural unit having a partial structure as shown in the above formula (1) as desired in the composition for forming a cured film of the present invention is preferably 1 to 2000 parts by mass based on 100 parts by mass of the compound as component (A), more preferably 5 to 1000 parts by mass.

[0169] [(C) Component]

[0170] The curing film forming composition of the present invention contains a cyclodextrin derivative with some or all of its hydroxyl groups modified as component (C).

[0171] Examples of cyclodextrin derivatives in which some or all of the hydroxyl groups of component (C) are modified include methyl-α-cyclodextrin, methyl-β-cyclodextrin, and methyl-γ-cyclodextrin, as well as methylated cyclodextrins such as methyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3-dihydroxypropyl-β-cyclodextrin, and 2,3-dihydroxypropyl-γ-cyclodextrin, etc.

[0172] In the curing film forming composition of the present invention, the compound of component (C) can be used in powder form or in solution form by dissolving the refined powder in the solvent described below.

[0173] Furthermore, in the composition for forming a cured film of the present invention, the compound as component (C) may also be a mixture of various compounds included in the definition of component (C).

[0174] The content of the compound as component (C) in the curing film forming composition of the present invention is preferably 10 parts to 1000 parts by mass, more preferably 30 parts to 500 parts by mass, based on 100 parts by mass of the photo-orientation component as component (A).

[0175] [(D) component]

[0176] In addition to components (A), (B) and (C) mentioned above, the composition for forming a cured film of the present invention may also contain a crosslinking catalyst as component (D).

[0177] Regarding the crosslinking catalyst as component (D), examples include acids or thermally generated acid agents. This component (D) is effective in promoting the thermal curing reaction during the formation of the cured film using the curing film forming composition of the present invention.

[0178] When using an acid or a thermally generated acid agent as component (D), component (D) is not particularly limited as long as it is a compound containing a sulfonic acid group, hydrochloric acid or its salt, a compound that produces acid by thermal decomposition during pre-baking or post-baking, that is, a compound that produces acid by thermal decomposition at a temperature of 60°C to 250°C.

[0179] Examples of such compounds include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentasulfonic acid, octylsulfonic 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-perfluorooctylsulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, 1,2-ethanedisulfonic acid, methanesulfonic anhydride, and other sulfonic acids or their hydrates and salts.

[0180] In addition, examples of compounds that produce acids through heat include, for example, bis(toluenesulfonyloxy)ethane, bis(toluenesulfonyloxy)propane, bis(toluenesulfonyloxy)butane, p-nitrobenzyltoluenesulfonate, o-nitrobenzyltoluenesulfonate, 1,2,3-phenylenetris(methylsulfonate), and p-toluenesulfonic acid pyridine. Salt, p-toluenesulfonate morpholine Salts, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenyl ethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-4-toluenesulfonamide, and compounds represented by formulas [TAG-1] to [TAG-41] below.

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188] The above-mentioned ingredient (D) is available as a commercially available product, for example, TA-100, TA-100FG, IK-1, IK-1FG (and above). (manufactured by) (Company) (Registered Trademark) SI-B2A (Registered Trademark) SI-B7 (Registered Trademark) SI-B3A (Registered Trademark) SI-B3 (Registered Trademark) SI-B5 (Registered Trademark) SI-B4 (Registered Trademark) SI-150 (Registered Trademark) SI-110 (Registered Trademark) SI-60 (Registered Trademark) SI-80 (Registered trademark) SI-100 (or above, manufactured by Sanshin Chemical Industry Co., Ltd.), etc.

[0189] The content of component (D) in the curable film forming composition of the present invention is 0.01 to 20 parts by mass relative to 100 parts by mass of the photo-alignment component (A), preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and even more preferably 0.1 to 6 parts by mass. By making the content of component (D) 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted, as well as high sensitivity to exposure. In addition, by making it 20 parts by mass or less, the curable film forming composition can have good storage stability.

[0190] [(E) component]

[0191] The curing film forming composition of the present invention may also contain a component (hereinafter also referred to as an adhesion-enhancing component) that improves the adhesion of the formed curing film as component (E).

[0192] The adhesion-enhancing component (E) can covalently link the polymeric functional groups of the polymeric liquid crystal with the crosslinking reaction sites of the alignment material, thereby improving the adhesion between the alignment material and the polymeric liquid crystal layer obtained from the curing film forming composition of the present invention. As a result, the phase retardation material of this embodiment, formed by laminating and curing the polymeric liquid crystal on the alignment material of this embodiment, can maintain strong adhesion even under high temperature and high humidity conditions, and can exhibit high durability against peeling and the like.

[0193] As component (E), monomers and polymers having groups selected from hydroxyl and N-alkoxymethyl groups and polymerizable groups are preferred.

[0194] Examples of such (E) components include compounds having hydroxyl and (meth)acryloyl groups, compounds having N-alkoxymethyl and (meth)acryloyl groups, and polymers having N-alkoxymethyl and (meth)acryloyl groups. Specific examples are shown below.

[0195] As an example of component (E), polyfunctional acrylates containing hydroxyl groups (hereinafter also referred to as hydroxyl-containing polyfunctional acrylates.)

[0196] Examples of hydroxyl-containing polyfunctional acrylates that are components of (E) include, for example, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

[0197] As an example of component (E), compounds having one acryloyl group and one or more hydroxyl groups can also be cited.

[0198] The following compounds can be cited as specific examples of compounds having one acryloyl group and one or more hydroxyl groups.

[0199]

[0200] (In the above formula, R) 11 (This represents a hydrogen atom or a methyl group, where m represents an integer from 1 to 10.)

[0201] In addition, as a component (E), a compound may be cited as having at least one polymeric group containing a C=C double bond and at least one N-alkoxymethyl group in one molecule.

[0202] Examples of polymerizable groups containing C=C double bonds include acryloyl, methacryloyl, vinyl, allyl, and maleimide.

[0203] As a compound having at least one polymerizable group containing a C=C double bond and at least one N-alkoxymethyl group in one molecule, the compound shown in the following formula (X1) is preferably an example.

[0204]

[0205] (In formula (X1), R) 31 R represents a hydrogen atom or a methyl group. 32 (representing hydrogen atoms, or alkyl groups with 1 to 10 carbon atoms in a straight or branched chain)

[0206] Specific examples of the compounds shown in formula (X1) above include N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, and other acrylamide compounds or methacrylamide compounds in which hydroxymethyl or alkoxymethyl groups have been substituted. It should be noted that (meth)acrylamide refers to both methacrylamide and acrylamide.

[0207] Another preferred manner for (E) is a compound having a polymeric group containing a C=C double bond and an N-alkoxymethyl group, such as the compounds described below.

[0208]

[0209] The content of component (E) in the liquid crystal alignment agent curing film forming composition according to the embodiments of the present invention is preferably 1 to 300 parts by mass relative to 100 parts by mass of the alignment component as component (A), and more preferably 5 to 200 parts by mass.

[0210] [Other Additives]

[0211] The composition for forming a cured film of the present invention may contain other additives, provided that the effect of the present invention is not compromised.

[0212] Other additives may include, for example, sensitizers. Sensitizers are effective in promoting the photoreaction of the surface of the optical film formed in this invention.

[0213] Examples of sensitizers include derivatives of benzophenone, anthracene, anthraquinone, and thioxanthone, as well as nitrophenyl compounds. Among these, N,N-diethylaminobenzophenone, a derivative of benzophenone, and 2-nitrofluorene, 2-nitrofluorene ketone, 5-nitrodihydroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, and 4-nitro[…]. 4-Nitrobenzophenone, 5-Nitroindole.

[0214] These sensitizers are not specifically limited to the substances mentioned above. They can be used alone or in combination with two or more compounds.

[0215] In embodiments of the present invention, the proportion of the sensitizer used relative to 100 parts by weight of component (A) is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight. If the proportion is too small, the effect as a sensitizer may not be fully obtained; if the proportion is too large, the transmittance of the cured film may be reduced or the coating may be rough.

[0216] Furthermore, as long as the effects of the present invention are not compromised, the composition for forming a cured film of the present invention may contain silane coupling agents, surfactants, rheology modifiers, pigments, dyes, preservation stabilizers, defoamers, antioxidants, etc., as other additives.

[0217] [solvent]

[0218] The curing film forming composition of the present invention is often used in a solution state dissolved in a solvent. At this time, the solvent used is not particularly limited in type or structure, as long as it is capable of dissolving component (A), component (B), component (C), component (D), component (E) as needed, and other additives.

[0219] Specific examples of solvents include, for instance, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, cyclopentyl methyl ether, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, and 2-hydroxyl group. Ethyl propionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxylate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, n-propyl acetate, isopropyl acetate, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone, etc.

[0220] Solvents are available as commercially available products; for example, (Registered Trademark) PM (Registered Trademark) MIP (Registered Trademark) IPM (Registered Trademark) IPE (Registered Trademark) PHI (Registered Trademark) MHI (Registered Trademark) PIP (Registered Trademark) HIMTE (Registered Trademark) PHM (Registered Trademark) IPME (Registered trademark) P-7 (and above, manufactured by Daishin Chemical Co., Ltd.), etc.

[0221] These solvents can be used alone or in combination of two or more. Among these solvents are 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, and methyl 3-ethoxypropionate. (Registered Trademark) IPM is a better choice due to its excellent film-forming properties and high safety.

[0222] <Preparation of Compositions for Curing Films>

[0223] As described above, the curable film forming composition of the present invention is a substance obtained by dissolving a photo-orientation component (A), a polymer having structural units having N-hydroxymethyl or N-alkoxymethyl groups as component (B), and structural units having a partial structure as shown in formula (1) as desired, a cyclodextrin derivative modified with some or all of its hydroxyl groups as component (C), and a crosslinking catalyst as component (D) as desired, in a solvent. Further, a bonding-enhancing component as component (E) may be included as desired. Furthermore, other additives may be included as long as the effects of the present invention are not impaired.

[0224] Preferred examples of the composition for forming a cured film according to the present invention are shown below.

[0225] [1]: A composition for forming a cured film, comprising (A) a photo-aligning component, (B) a component of 1 to 2000 parts by mass based on 100 parts by mass of (A) a component of 10 to 1000 parts by mass based on 100 parts by mass of (A) a component of (C).

[0226] [2]: A composition for forming a cured film, comprising (A) a photo-aligning component, (B) a component of 1 to 2000 parts by mass based on 100 parts by mass of (A), (C) a component of 10 to 1000 parts by mass based on 100 parts by mass of the photo-aligning component of (A), and (D) a crosslinking catalyst of 0.01 to 20 parts by mass relative to 100 parts by mass of (A).

[0227] [3]: A composition for forming a cured film, comprising (A) a photo-aligning component, (B) a component in the amount of 1 to 2000 parts by mass based on 100 parts by mass of (A), (C) a component in the amount of 10 to 1000 parts by mass based on 100 parts by mass of (A), (D) a crosslinking catalyst in the amount of 0.01 to 20 parts by mass relative to 100 parts by mass of (A), and (E) a component in the amount of 1 to 300 parts by mass based on 100 parts by mass of (A).

[0228] The following details the mixing ratio, preparation method, etc., when the curing film forming composition of the present invention is used in solution form.

[0229] Regarding the proportion of solid components in the curing film forming composition of the present invention, there is no particular limitation as long as each component is uniformly dissolved in the solvent, but it is 1% to 80% by mass, preferably 2% to 60% by mass, and more preferably 3% to 40% by mass. Here, solid components refer to components from all components of the curing film forming composition after the solvent has been removed.

[0230] The method for preparing the composition for forming the cured film of the present invention is not particularly limited. Examples of preparation methods include, for instance, mixing components (A) and (C) in a solution of component (B) dissolved in a solvent in a predetermined proportion, preparing a homogeneous solution according to desired component (D) and desired component (E), or further adding other additives as needed at an appropriate stage of the preparation method.

[0231] In the preparation of the curing film forming composition of the present invention, a solution of the specific polymer 2 (component (B)) obtained by polymerization in a solvent can be used directly, as described above. In this case, for example, to a solution of component (B) obtained by copolymerizing the aforementioned monomer having N-hydroxymethyl or N-alkoxymethyl with a monomer having a group shown in formula (1) and a monomer other than the desired monomer, component (A), component (C), and further, components (D), (E), etc., as desired, are added to form a homogeneous solution. At this time, additional solvent may be added for the purpose of adjusting the concentration. At this time, the solvent used in the manufacturing process of component (B) and the solvent used to adjust the concentration of the curing film forming composition may be the same or different.

[0232] Furthermore, the solution of the prepared curing film forming composition is preferably filtered using a filter with a pore size of about 0.2 μm before being used to form a curing film.

[0233] <Curated films, alignment materials, and phase difference materials>

[0234] A coating film is formed by applying a solution of the curing film forming composition of this embodiment onto a substrate (e.g., a silicon / silica coated substrate, a silicon nitride substrate, a substrate coated with metals such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, an ITO substrate, etc.) or a film (e.g., a triacetyl cellulose (TAC) film, a cyclic olefin polymer film, a polyethylene terephthalate film, an acrylic film, etc.) through methods such as rod coating, spin coating, flow coating, roll coating, slot coating, slot-post spin coating, inkjet coating, or printing. Then, a curing film is formed by heating and drying with a heating plate or an oven.

[0235] As for the heating and drying conditions, when using a cured film as a liquid crystal alignment film, the curing reaction can proceed to the extent that the components of the liquid crystal alignment film do not dissolve in the polymeric liquid crystal solution coated thereon. For example, a heating temperature and heating time appropriately selected from the range of 50°C to 200°C and 0.4 minutes to 60 minutes can be used. The preferred heating temperature and heating time are 60°C to 160°C and 0.5 minutes to 10 minutes.

[0236] The thickness of the cured film obtained using the curing film forming composition of the present invention is, for example, 0.05 μm to 5 μm, and can be appropriately selected by taking into account the height difference, optical properties, and electrical properties of the resin film used as the substrate.

[0237] The cured film produced by this operation, using the curing film forming composition of the present invention, can be irradiated with polarized UV light, thereby enabling the cured film formed on the substrate to function as a liquid crystal alignment film, that is, to function as a component for orienting liquid crystal compounds including polymeric liquid crystals, and can be used as an alignment material.

[0238] As a method of irradiating polarized UV light, ultraviolet to visible light with wavelengths of 150nm to 450nm is typically used, and linearly polarized light is irradiated from a vertical or oblique direction at room temperature or under heated conditions.

[0239] In the alignment material of the present invention, the cured film that becomes the liquid crystal alignment film has solvent resistance and heat resistance. Therefore, after coating the alignment material with a phase difference material formed from a polymeric liquid crystal solution, the material is heated until the phase transition temperature of the liquid crystal, thereby aligning the phase difference material in a liquid crystal state on the alignment material. Furthermore, the phase difference material that has reached the desired alignment state can be directly cured to form a phase difference material having a layer with optical anisotropy.

[0240] As a phase retardation material, for example, liquid crystal monomers having polymerizable groups and compositions containing such liquid crystal monomers are used. Furthermore, in the case where the substrate for forming the alignment material is a film, the phase retardation material of the present invention is useful as a phase retardation film. The phase retardation material forming such a phase retardation material is in a liquid crystal state, and horizontal orientation, cholesterol-type orientation, vertical orientation, mixed orientation, etc., are formed on the alignment material, and can be used separately according to the desired phase retardation characteristics.

[0241] Furthermore, in the case of patterned retardant materials used in the manufacture of 3D displays, the surface of the cured film in the optical film of the present invention is exposed to polarized UV light from a predetermined reference, for example, at a +45-degree direction, through a mask with a line and gap pattern. Then, after removing the mask, polarized UV light is exposed at a -45-degree direction with less exposure. This makes the cured film on the surface of the film a liquid crystal alignment film forming two liquid crystal alignment regions with different alignment control directions, thus enabling the optical film to function as an alignment material. Then, after coating the retardant material formed from a polymeric liquid crystal solution onto the alignment material, it is heated to the phase transition temperature of the liquid crystal, thereby making the retardant material a liquid crystal state. The polymeric liquid crystal in the liquid crystal state aligns on the alignment material forming the two liquid crystal alignment regions, forming an alignment state corresponding to each liquid crystal alignment region. Furthermore, the retardant material achieving such an alignment state can be directly cured, fixing the aforementioned alignment state, resulting in a patterned retardant material in which multiple phase difference regions with different phase difference characteristics are regularly arranged.

[0242] The cured film obtained using the curing film forming composition of the present invention can also be used as a liquid crystal alignment film for a liquid crystal display element. For example, an optical film of this embodiment formed as described above can be used, and after bonding the alignment materials in the two optical films to each other via spacers, liquid crystal can be injected between these substrates to manufacture a liquid crystal aligned liquid crystal display element.

[0243] Therefore, the curing film forming composition of the present invention is suitable for use in manufacturing various phase retardation materials (phase retardation films), liquid crystal display elements, etc.

[0244] Example

[0245] The present invention will be specifically described below with examples of its embodiments, but the invention is not limited thereto.

[0246] [Abbreviations used in the examples]

[0247] The meanings of the abbreviations used in the following embodiments are as follows.

[0248] <Ingredients>

[0249] BMAA: N-Butoxymethylacrylamide

[0250] BMMA: N-Butoxymethylmethacrylamide

[0251] AAEM: Ethyl methacrylate (2-acetylacetoxy) (a monomer having the group shown in formula (1))

[0252] 4HBA: 4-Hydroxybutyl acrylate

[0253] HEMA: 2-Hydroxyethyl methacrylate

[0254] TGL: α-Thioglycerol

[0255] MAIB: 2,2'-Azobis(isobutyric acid) dimethyl ester

[0256] <Component A

[0257] MCA: 4-Methoxycinnamic acid

[0258] M6CA: 4-(6-Methacryloyloxyhexyl-1-oxy)cinnamic acid

[0259] PCA: 4-Propoxycinnamic acid

[0260] 6CAM: Methyl 4-(6-hydroxyhexyloxy)cinnamate

[0261] 6MCAM: Methyl 3-methoxy-4-(6-hydroxyhexyloxy)cinnamate

[0262] \(6BP\): tert-Butyl 4-[4-(6-hydroxyhexyloxy)benzoyl]cinnamate

[0263] HCA: 4-Hydroxycinnamic acid

[0264] <Component C

[0265] HCD: 2-Hydroxypropyl-β-cyclodextrin( (manufactured by Wako Pure Chemical Industries, Ltd., CAVASOL W7HP (registered trademark))

[0266] MCD: Methyl-β-cyclodextrin (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0267] <Component D: Crosslinking catalyst

[0268] PPTS: Pyridinium p-toluenesulfonate

[0269] PTSA: p-Toluenesulfonic acid monohydrate

[0270] CSA: (±)-10-Camphorsulfonic acid

[0271] BSA: Benzenesulfonic acid monohydrate

[0272] <Component E: Component for improving adhesion

[0273] PET: Pentaerythritol triacrylate

[0274] <Other components

[0275] RDK: (Registered Trademark) RDK-133 (manufactured by Kawasaki Kasei Kogyo Co., Ltd., polyester polyol)

[0276] M926: (Registered Trademark) M-926 (manufactured by Toagosei Co., Ltd., special acrylate)

[0277] HPC: Hydroxypropyl cellulose (manufactured by Nippon Soda Co., Ltd., NISSO HPC SSL (Registered Trademark))

[0278] HMM:六甲氧基甲基三聚氰胺

[0279] <Solvent>

[0280] PM: Propylene glycol monomethyl ether

[0281] <Measurement of weight-average molecular weight>

[0282] Apparatus: GPC apparatus (HLC-8320) manufactured by Co., Ltd.

[0283] Column: TSKgel (Registered Trademark) α-4000 and TSKgel (Registered Trademark) α-3000 manufactured by Co., Ltd.

[0284] Column oven: 40 °C

[0285] Flow rate: 1 mL / min

[0286] Eluent: N,N-dimethylformamide

[0287] Standard sample: Polystyrene

[0288] <Synthesis of Component B>

[0289] (Synthesis Example 1)

[0290] After dissolving BMMA (135.0 g, 789 mmol), AAEM (8.89 g, 41.5 mmol), TGL (0.898 g, 8.30 mmol) as a chain transfer agent, and MAIB (5.73 g, 24.9 mmol) as a polymerization catalyst in PM (150.5 g), the solution was added dropwise to a flask containing PM (200.7 g) maintained at 70 °C over 60 minutes. After completion of the dropwise addition, the mixture was reacted for 5 hours to obtain a solution (PB-1) of an acrylic copolymer (BMMA / AAEM = 95 / 5 (molar ratio)) with a solid content concentration of 30% by mass. The weight-average molecular weight Mw of the obtained acrylic copolymer was 26,400.

[0291] (Synthesis Example 2)

[0292] BMMA (9.00 g, 52.6 mmol), AAEM (1.25 g, 5.84 mmol), TGL (63.2 mg, 0.580 mmol) as a chain transfer agent, and MAIB (0.404 g, 1.75 mmol) as a polymerization catalyst were dissolved in PM (11.2 g), and then the solution was added dropwise to a flask maintained at 70 °C and containing PM (15.0 g) over 60 minutes. After completion of the dropwise addition, the mixture was reacted for 5 hours to obtain a solution (PB-2) of an acrylic copolymer (BMMA / AAEM = 90 / 10 (molar ratio)) (solid content concentration: 30% by mass). The weight-average molecular weight Mw of the obtained acrylic copolymer was 26,000.

[0293] (Synthesis Example 3)

[0294] BMMA (7.00 g, 40.9 mmol), AAEM (3.76 g, 17.5 mmol), TGL (63.2 mg, 0.580 mmol) as a chain transfer agent, and MAIB (0.404 g, 1.75 mmol) as a polymerization catalyst were dissolved in PM (11.2 g), and then the solution was added dropwise to a flask maintained at 70 °C and containing PM (15.0 g) over 60 minutes. After completion of the dropwise addition, the mixture was reacted for 5 hours to obtain a solution (PB-3) of an acrylic copolymer (BMMA / AAEM = 70 / 30 (molar ratio)) (solid content concentration: 30% by mass). The weight-average molecular weight Mw of the obtained acrylic copolymer was 26,000.

[0295] (Synthesis Example 4)

[0296] BMMA (145.00 g, 847 mmol), TGL (0.916 g, 8.47 mmol) as a chain transfer agent, and MAIB (5.85 g, 25.4 mmol) as a polymerization catalyst were dissolved in PM (151 g), and then the solution was added dropwise to a flask maintained at 70 °C and containing PM (202 g) over 60 minutes. After completion of the dropwise addition, the mixture was reacted for 5 hours to obtain a solution (PB-4) of an acrylic polymer (solid content concentration: 30% by mass). The weight-average molecular weight Mw of the obtained acrylic copolymer was 26,400.

[0297] (Synthesis of Comparative Compound of Component C)

[0298] (Synthesis Example 5)

[0299] 4HBA (197.0 g, 1.37 mol) and MAIB (3.1 g, 13 mmol) as a polymerization catalyst were dissolved in PM (133.4 g). This solution was then added dropwise over 2 hours to a flask containing PM (166.8 g) maintained at 70 °C. After the addition was complete, the reaction was allowed to proceed for 18 hours to obtain a solution of the acrylic polymer (PC'-1) (solids concentration 40% by mass). The weight-average molecular weight (Mw) of the obtained acrylic polymer was 22,700.

[0300] (Synthesis Example 6)

[0301] HEMA (197.0 g, 1.51 mol) and MAIB (3.5 g, 15 mmol) as a polymerization catalyst were dissolved in PM (133.7 g). This solution was then added dropwise over 2 hours to a flask containing PM (167.1 g) maintained at 70 °C. After the addition was complete, the reaction was allowed to proceed for 18 hours to obtain a solution of the acrylic polymer (PC'-2) (solids concentration 40% by mass). The weight-average molecular weight (Mw) of the obtained acrylic polymer was 25,000.

[0302] <Preparation of Compositions for Curing Films>

[0303] (Example 1-1)

[0304] MCA (0.1 g, 14 parts by mass) as component (A), PB-1 solution (1.4 g, 60 parts by mass) obtained in Synthesis Example 1 as component (B), and HCD (0.2 g, 26 parts by mass) as component (C) were mixed, and PM (7.3 g) as solvent was added. The mixture was stirred for 2 hours, and the solution was obtained by visual confirmation that it had dissolved. The resulting solution was then filtered through a filter with a pore size of 0.2 μm to prepare a composition (A-1) with a solid content concentration of 8.0% by mass.

[0305] (Examples 1-2 to 1-36, Comparative Examples 1-1 to 1-16)

[0306] Using the ingredients of the types and mixing amounts shown in Table 1 below, except that the same procedure is followed as in Example 1-1, to prepare (A-2)~(A-36) and (B-1)~(B-16).

[0307] [Table 1]

[0308]

[0309] <Preparation of Catalyst Solution>

[0310] (Modulation Example 1)

[0311] PPTS (1.0 g) as a catalyst and PM (19.0 g) as a solvent were added and stirred for 1 hour until dissolution was visually confirmed. The solution was then filtered through a 0.2 μm filter to prepare the catalyst solution (D-1).

[0312] (Modulation Example 2)

[0313] PTSA (1.0 g) as a catalyst and PM (19.0 g) as a solvent were added and stirred for 1 hour until dissolution was visually confirmed. The solution was then filtered through a 0.2 μm filter to prepare the catalyst solution (D-2).

[0314] (Modulation Example 3)

[0315] Add CSA (2.0 g) as a catalyst and PM (18.0 g) as a solvent, and stir for 1 hour until dissolution is visually confirmed. Filter the solution through a 0.2 μm filter to prepare the catalyst solution (D-3).

[0316] (Modulation Example 4)

[0317] Add BSA (1.0 g) as a catalyst and PM (19.0 g) as a solvent, and stir for 1 hour until dissolution is visually confirmed. Filter the solution through a 0.2 μm filter to prepare the catalyst solution (D-4).

[0318] Modulation of liquid crystal alignment agent

[0319] (Example 2-1)

[0320] Add D-1 (0.12g) obtained in Modulation Example 1 and PM (0.54g) as a diluent to A-1 (2.00g) obtained in Example 1-1, and stir for 1 minute to obtain liquid crystal alignment agent AL-1.

[0321] (Examples 2-2 to 2-39, Comparative Examples 2-1 to 2-16)

[0322] Using the components of the types shown in Table 2 below, except that the same procedure was followed as in Example 2-1, liquid crystal alignment agents (AL-2)~(AL-39) and (BL-1)~(BL-16) were obtained.

[0323] [Table 2]

[0324]

[0325] <Preparation of Polymerizable Liquid Crystal Solution for Horizontal Orientation>

[0326] Paliocolor (registered trademark) LC-242 (BASF) is added as a polymeric liquid crystal for horizontal alignment. (manufactured by (Company)) (19.8g), Omnirad (registered trademark) 907 (manufactured by IGM Resins BV) as a photoradical initiator (1.0g), BYK (registered trademark)-361N as a leveling agent ( (0.06g) was prepared by (Company Name), and cyclopentanone (79g) was added as a solvent. The mixture was stirred for 2 hours and visually confirmed to be dissolved, resulting in a polymeric liquid crystal solution (LC-1) with a solid content concentration of 20% by mass.

[0327] <Formation of Liquid Crystal Alignment Films and Fabrication of Phase Retardation Films>

[0328] (Example 3-1)

[0329] The liquid crystal alignment agent (AL-1) obtained in Example 2-1 was coated onto the TAC film, which served as the substrate, with a wet film thickness of 4 μm using a rod coater. The film was then heated and dried at 120°C for 2 minutes in a hot air circulating oven to form a cured film. Next, linearly polarized light with a wavelength of 313 nm was applied at 20 mJ / cm². 2 The exposure amount was vertically irradiated onto the surface of the cured film, forming a liquid crystal alignment film. A horizontally aligned polymerizable liquid crystal solution LC-1 was then coated onto the liquid crystal alignment film with a wet film thickness of 10 μm using a rod coater. Next, it was heated and dried in an oven at 100°C for 2 minutes, and then subjected to unpolarized light at a wavelength of 365 nm at 400 mJ / cm² under nitrogen atmosphere. 2 The exposure amount is vertically irradiated, thereby solidifying the polymeric liquid crystal to produce a phase retardation film (S-1).

[0330] (Examples 3-2 to 3-40, Comparative Examples 3-1 to 3-16)

[0331] By changing the type of liquid crystal alignment agent and the type of film on the substrate as shown in Table 3 below, the same procedure as in Example 3-1 was followed to produce phase retardation films (S-2) to (S-40) and (R-1) to (R-16).

[0332] The phase difference films produced as described above were evaluated using the following methods. The evaluation results are shown in Table 3.

[0333] [Evaluation of Liquid Crystal Orientation]

[0334] The phase difference films obtained in Examples 3-1 to 3-40 and Comparative Examples 3-1 to 3-16 were sandwiched between a pair of polarizing plates, and the performance of the phase difference characteristics under a cross prism was observed visually. As an evaluation criterion, the case where the phase difference was performed without defects was defined as "○", and the case where the phase difference was not performed was defined as "×". The results are shown in Table 3.

[0335] [Evaluation of Liquid Crystal Rejection]

[0336] The phase difference films obtained in Examples 3-1 to 3-40 and Comparative Examples 3-1 to 3-16 were sandwiched between a pair of polarizing plates. The phase difference characteristics under the cross prism were observed visually, and the absence of liquid crystal layer repulsion within the central 50×50mm area was defined as "○", and the occurrence of liquid crystal layer repulsion was defined as "×". The results are shown in Table 3.

[0337] [Table 3]

[0338]

[0339] As shown in Table 3, the phase retardation films (Examples 3-1 to 3-40) obtained from the curing film forming compositions containing components (A), (B), and (C) all exhibited no liquid crystal repulsion and good orientation. Furthermore, the phase retardation films (Examples 3-40) obtained from the curing film forming compositions containing components (A), (B), (C), and (E) also exhibited no liquid crystal repulsion and good orientation and adhesion. In contrast, the phase retardation films (Comparative Examples 3-1, 3-15 to 3-16) obtained from the curing film forming compositions not containing component (B) showed poor liquid crystal orientation, and the phase retardation films (Comparative Examples 3-2 to 3-14) obtained from the curing film forming compositions not containing component (C) all exhibited liquid crystal repulsion, resulting in suboptimal phase retardation films.

[0340] [Evaluation of fit]

[0341] The surface of the phase retardation film (the surface of the layer forming the polymeric liquid crystal) obtained in Examples 3-40 and Comparative Examples 3-1 to 3-16 was divided into squares (1 mm × 1 mm × 100 squares) using a cutter, and then celluloid tape was attached. Company (Registered trademark), 24mm width). Next, when the celluloid tape was peeled off, the number of squares remaining on the underlying cured film and the further underlying film substrate without peeling off were counted. All remaining cases were defined as "○", partial peeling as "△", and complete peeling as "×", and the results were evaluated. The phase retardation films obtained in Comparative Examples 3-1 to 3-16 were "×", but the phase retardation films obtained in Examples 3-40 were "○", indicating that the phase retardation film obtained from the curing film forming composition containing component (E) in addition to components (A), (B), and (C) exhibits good adhesion.

Claims

1. A composition for forming a cured film, comprising: Component A: Compounds with photooriented groups. Component B: Polymers possessing structural units having N-hydroxymethyl or N-alkoxymethyl groups, and Component C: Cyclodextrin derivatives with some or all of their hydroxyl groups modified.

2. The composition for forming a cured film according to claim 1, characterized in that, The photo-orientation group of component A is a functional group that performs photodimerization or photoisomerization.

3. The composition for forming a cured film according to claim 1, characterized in that, The photo-orientation group of component A is cinnamoyl.

4. The composition for forming a cured film according to claim 1, characterized in that, The photo-orientation group of component A is a group with an azobenzene structure.

5. The composition for forming a cured film according to claim 1, Component B is a polymer that also possesses structural units having the partial structure shown in formula (1) below. In formula (1), Q1 represents an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or a phenyl group; Q2 represents O, S, or NQ3; Q3 is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms; and the dashed line represents a bonding bond.

6. The composition for forming a cured film according to claim 1, characterized in that, It also contains a cross-linking catalyst as component D.

7. The composition for forming a cured film according to claim 1, characterized in that, It also contains a binding-enhancing ingredient as component E.

8. An oriented material, characterized in that, It is obtained using the composition for forming a cured film according to any one of claims 1 to 7.

9. A phase difference material, characterized in that, It is formed using a cured film obtained from the composition for forming a cured film according to any one of claims 1 to 7.

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