Resin composition for thermosetting photo-alignment film

Abstract

The present invention addresses the problem of providing a composition for forming a cured film, which is capable of sufficiently reducing the formaldehyde concentration in a liquid composition and suppressing an increase in formaldehyde over time. [Solution] A composition for forming a cured film, which 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 a structural unit having a partial structure represented by formula (1); and (D) a crosslinking catalyst. (In formula (1), Q1 represents an alkyl group having 1-6 carbon atoms, an alkoxy group having 1-6 carbon atoms, or a phenyl group, Q2 represents O, S, or NQ3, Q3 represents a hydrogen atom or an alkyl group having 1-4 carbon atoms, and the dotted line represents a bond. )

Description

Technical Field

[0001] This invention relates to a resin composition for thermosetting photoalignment films (also known as a composition for curing film formation), alignment elements, and phase difference elements. Background Technology

[0002] In the case of 3D displays using circularly polarized glasses, a phase difference element is typically disposed on the display element that forms the image, such as a liquid crystal panel. This phase difference element has multiple regularly arranged phase difference regions with different phase difference characteristics, forming a patterned phase difference element. It should be noted that, hereinafter, in this specification, such a phase difference element patterned by arranging multiple phase difference regions with different phase difference characteristics is referred to as a patterned phase difference element.

[0003] Patterned retardation elements, as disclosed in, for example, Patent Document 1, can be fabricated by optically patterning a retardation material composed of polymeric liquid crystal. The optical patterning of the retardation material composed of polymeric liquid crystal utilizes photoalignment techniques known in the formation of alignment elements in liquid crystal panels. Specifically, a coating film formed of a photoalignable material is formed on a substrate, and two polarized lights with different polarization directions are irradiated onto it. A photoalignment film is then obtained as an alignment element forming two liquid crystal alignment regions with different alignment control directions. A solution-like retardation material containing polymeric liquid crystal is coated onto this photoalignment film to achieve the alignment of the polymeric liquid crystal. Then, the aligned polymeric liquid crystal is cured to form a patterned retardation element.

[0004] The anti-reflective film of an organic EL display consists of a linear polarizer and a quarter-wavelength retardation plate. Incoming light heading towards the image display panel is converted into linearly polarized light by the linear polarizer, and then further converted into circularly polarized light by the quarter-wavelength retardation plate. Here, although the circularly polarized incoming light is reflected at the surface of the image display panel, the rotation direction of the polarization plane is reversed during this reflection. As a result, the reflected light, in the opposite direction to its arrival, is converted into linearly polarized light in the direction blocked by the linear polarizer after passing through the quarter-wavelength retardation plate. This significantly suppresses outward emission.

[0005] Regarding the quarter-wavelength retardation plate, Patent Document 2 proposes a method for constructing the optical film by combining a half-wavelength plate and a quarter-wavelength plate to form a quarter-wavelength retardation plate, thereby utilizing the inverse dispersion characteristic. In this method, an optical film can be constructed using a liquid crystal material with positive dispersion characteristics to utilize the inverse dispersion characteristic across a wide wavelength range for displaying color images.

[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, the phase retardation layer can be constructed with a single layer instead of two phase retardation layers formed by combining a 1 / 2 wavelength plate and a 1 / 4 wavelength plate to ensure the 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 parts 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] Furthermore, in photoaligning agents using the cinnamic yl group, there are examples where thermal crosslinking has been introduced to improve alignment sensitivity and impart solvent resistance (see Patent Documents 8 and 9).

[0010] In addition, Patent Document 10 describes a thermosetting liquid crystal alignment member using a resin composition having N-alkoxymethyl groups as a highly sensitive photoalignment agent.

[0011] However, compounds containing N-hydroxymethyl groups are obtained through the reaction of amino groups with formaldehyde to form N-hydroxymethyl groups, and therefore theoretically often contain trace amounts of formaldehyde. Formaldehyde was designated a hazardous substance under the Hazardous Substances Control Act as of April 2023, and is highly toxic to living organisms. Furthermore, it has been identified as carcinogenic by the International Agency for Research on Cancer. Furthermore, formaldehyde is released into the air from compounds used in building materials and furniture, contributing to the problem of sick building syndrome. Therefore, when using compounds containing at least one of N-hydroxymethyl and N-alkoxymethyl groups in articles, it is necessary to reduce the formaldehyde concentration in the composition to ensure the safety of manufacturers and consumers, and especially for molded articles and coatings, it is necessary to suppress the release into the gas phase and liquid layer.

[0012] Existing technical documents

[0013] Patent documents

[0014] Patent Document 1: Japanese Patent Application Publication No. 2005-49865

[0015] Patent Document 2: Japanese Patent Application Publication No. 10-68816

[0016] Patent Document 3: US Patent No. 8,119,026

[0017] Patent Document 4: Japanese Patent Application Publication No. 2009-179563

[0018] Patent Document 5: Japanese Patent No. 3611342

[0019] Patent Document 6: Japanese Patent Application Publication No. 2009-058584

[0020] Patent Document 7: Japanese Patent Publication No. 2001-517719

[0021] Patent Document 8: International Patent Application Publication No. WO2011 / 126022

[0022] Patent Document 9: International Patent Application Publication No. WO2014 / 010688

[0023] Patent Document 10: WO2010 / 150748 Summary of the Invention

[0024] The problem that the invention aims to solve

[0025] When thermal crosslinking is introduced into the cured film, there is a concern about the generation of formaldehyde. For example, for compositions used in the formation of cured films that employ crosslinking agents containing N-hydroxymethyl, N-alkoxymethyl, etc., there is a need for a simple method to suppress the generation of formaldehyde.

[0026] Furthermore, for formaldehyde scavengers marketed for the purpose of reducing formaldehyde in liquid compositions, adding several percent to up to about 20% to the composition may significantly reduce the composition's functionality. Moreover, in the case of adding multiple components, the greater the variety of added components, the higher the risk of negatively impacting the composition's inherent performance.

[0027] Therefore, a method is required that can sufficiently reduce the amount of formaldehyde contained in the composition for curing film formation even when the amount of formaldehyde scavenger added is extremely small. Furthermore, a method is required that can sufficiently reduce the amount of formaldehyde in the liquid composition by adding a formaldehyde scavenger, and that the formaldehyde content does not increase over time. A method is further required that can sufficiently reduce formaldehyde in liquid compositions, particularly liquid compositions containing compounds having at least one of N-hydroxymethyl and N-alkoxymethyl groups.

[0028] This invention is based on the above understanding and research results. Specifically, the object of this invention is to provide a method for reducing formaldehyde in a liquid composition and a method for manufacturing the liquid composition using this method.

[0029] Methods for solving problems

[0030] In order to achieve the above-mentioned objectives, the inventors have repeatedly conducted in-depth research and found that by including a process of copolymerizing a monomer having a partial structure with a specific formaldehyde-capturing effect with a monomer that becomes a formaldehyde-generating source, even a small copolymerization ratio can sufficiently reduce the formaldehyde concentration in the liquid composition and suppress the increase of formaldehyde over time. The present invention with the following objectives has been completed.

[0031] That is, the present invention includes the following solutions.

[0032] [1] A composition for forming a cured film, comprising: (A) Components: Compounds with photooriented groups; (B) Components: Polymer, wherein the polymer comprises: structural units having N-hydroxymethyl or N-alkoxymethyl, and structural units having a partial structure as shown in formula (1); and (D) Component: Crosslinking catalyst.

[0033]

[0034] (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.)

[0035] [2] In the composition for forming a cured film according to [1] above, the photo-orientation group of component (A) is a functional group that undergoes photodimerization or photoisomerization.

[0036] [3] In the composition for forming a cured film according to [1] above, the photo-orientation group of component (A) is cinnamoyl.

[0037] [4] In the composition for forming a cured film according to [1] above, the photo-orientation group of component (A) is a group with an azobenzene structure.

[0038] [5] The composition for forming a cured film according to [1] above contains an ammonium salt as component (C).

[0039] [6] In the composition for forming a cured film described in [5] above, the ammonium salt is ammonium acetate.

[0040] [7] An orientation member obtained by using the curing film forming composition described in any one of [1] to [6] above.

[0041] [8] A phase difference element is formed using a cured film obtained from any of the curing film forming compositions described in any one of [1] to [6] above.

[0042] The effects of the invention

[0043] According to the present invention, the formaldehyde concentration in the liquid composition can be sufficiently reduced, and the increase of formaldehyde over time can be suppressed. Detailed Implementation

[0044] The present invention will now be described in detail. It should be noted that the following description of the constituent elements is merely illustrative and the invention is not limited to these descriptions.

[0045] <Composition for Curing Film Formation>

[0046] The curing film forming composition of the present invention is a curing film forming composition comprising (A) a compound having a photooriented group, (B) a polymer and (D) a crosslinking catalyst, wherein the polymer has: a structural unit having an N-hydroxymethyl or N-alkoxymethyl group and a structural unit having a partial structure shown in formula (1).

[0047] The following is a detailed description of each ingredient.

[0048] [(A)Component]

[0049] 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; in this specification, component (A) is also referred to as a photoorientation component.

[0050] <Low molecular weight compounds with photooriented and thermally crosslinked groups>

[0051] 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.

[0052] 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.).

[0053] 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.

[0054] Furthermore, the so-called low-molecular-weight compound of component (A) can have a photoisomerization structural site that acts as a photooriented group. This refers to a structural site that changes between the cis and trans forms upon light irradiation. Specific examples include sites composed of azobenzene structures, piracene structures, etc. Among these, the azobenzene structure is preferred due to its high reactivity.

[0055] 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.

[0056]

[0057] In the above formula, A 1 and A 2 Each can be used independently to represent a hydrogen atom or a methyl group.

[0058] 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, carbamate bonds, amino bonds, carbonyl bonds, or combinations thereof, or it can be a structure formed by multiple substituents connected by the aforementioned bonds.

[0059] 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 also be linked via single bonds, ether bonds, ester bonds, amide bonds, or urea bonds.

[0060] X 13It represents hydroxyl, mercapto, alkoxy with 1 to 10 carbon atoms, alkylthio with 1 to 10 carbon atoms, phenoxy, biphenyloxy, or phenyl.

[0061] 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.

[0062] X 15 This 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] The low molecular weight compound that is component (A) is preferably a compound in which the polymerizable group is bonded to a group formed by the combination of a photooriented site and a thermally reactive site as shown in formula (a-1) via a spacer group.

[0072]

[0073] (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.

[0074] 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.

[0075] The above R 101 In this mixture, hydroxyl and amino groups are preferred, with hydroxyl groups being particularly preferred.

[0076] 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.

[0077] 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.

[0078] The above are specific examples of low molecular weight photoorientation components that are components of (A), but are not limited to these.

[0079] 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.

[0080] <Polymers with photooriented and thermally crosslinked groups>

[0081] 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 as a photo-oriented group that performs photodimerization or photoisomerization, 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).

[0082] 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.

[0083] (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.

[0084] Examples of photodimerization sites include cinnamyl, chalcone, coumarin, and anthracene. Among these, cinnamyl is preferred considering its high transparency in the visible light region and high photodimerization reactivity. More preferred cinnamyl groups and substituents containing cinnamyl structures include the structures shown in Formula [1] or Formula [2]. It should be noted that in this specification, the term "cinnamyl group" and "substituents containing cinnamyl structures" also include groups with a naphthalene ring as the benzene ring in the cinnamyl group.

[0085]

[0086] 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 either a halogen atom or a cyano group.

[0087] 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, the alkyl, phenyl, biphenyl, or cyclohexyl group 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.

[0088] In the above formulas [1] and [2], A represents any one of formulas [A1], [A2], [A3], [A4], [A5] and [A6].

[0089] 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.

[0090] 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.

[0091] (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.

[0092] 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.

[0093] 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.

[0094] More preferably, monomers having a cinnamoyl group having the structure shown in formula [1] or formula [2] above, and monomers containing substituents of the cinnamoyl group structure. Specific examples of such monomers are those shown in formula [3] or formula [4] below.

[0095]

[0096] 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 either a halogen atom or a cyano group.

[0097] 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.

[0098] 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, the alkyl, phenyl, biphenyl, or cyclohexyl group 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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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)phthalic acid, etc. Monomers containing carboxyl groups, such as esters, 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, diethylaminomethyl methacrylate, and tert-butylaminoethyl methacrylate.

[0103] 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.

[0104] 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).

[0105] Specific examples of such monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

[0106] The following are specific examples of the aforementioned monomers, but the present invention is not limited to these.

[0107] 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 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.

[0108] 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.

[0109] 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.

[0110] Examples of the aforementioned styrene compounds include styrene, methylstyrene, chlorostyrene, and bromostyrene.

[0111] Examples of the aforementioned maleimide compounds include, for example, maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0112] 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.

[0113] 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).

[0114] Furthermore, by adding a solution of the specific copolymer obtained as described above to diethyl ether, water, or the like under stirring to allow it to redefine, and then filtering / washing the resulting precipitate, followed by drying at room temperature or by heating under normal or reduced pressure, a powder of the specific copolymer can be produced. This process removes polymerization initiators and unreacted monomers coexisting 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 redissolving the obtained powder in a solvent.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] 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.

[0120] 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, tricyclic [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. 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. Examples of unsaturated aromatic compounds include: imides, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N-succinimide-6-maleimide hexanoate, N-succinimide-3-maleimide propionate, and N-(9-acridyl)maleimide; exemplified by unsaturated aromatic compounds are styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; exemplified by conjugated diene compounds are... 1,3-Butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.; examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, etc.; examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, succinic acid, itaconic acid, etc.; examples of unsaturated dicarboxylic acid anhydrides include the anhydrides of the above-mentioned unsaturated dicarboxylic acids; examples of polymerizable unsaturated compounds other than those mentioned above include acrylonitrile, methacrylonitrile, vinyl chloride, 1,1-dichloroethylene, acrylamide, methacrylamide, vinyl acetate, etc.

[0121] 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.

[0122] 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.

[0123] Commercially available products can also be used as polymers with epoxy groups on the side chains. Examples of such commercially available products include EHPE3150, EHPE3150CE (and above, manufactured by Daicel Co., Ltd.), UG-4010, UG-4035, UG-4040, UG-4070 (and above, manufactured by Toa Synthetic Co., Ltd., ARUFON series), ECN-1299 (manufactured by Asahi Kasei Co., Ltd.), DEN431, DEN438 (and above, manufactured by Dookemical Co., Ltd.). jER-152 (manufactured by Mitsubishi Microelectronics Co., Ltd.), Etrusion N-660, N-665, N-670, N-673, N-695, N-740, N-770, N-775 (the above, manufactured by DIC Co., Ltd. (formerly Dainippon Chemical Industry Co., Ltd.)), EOCN-1020, EOCN-102S, EOCN-104S (the above, manufactured by Nippon Kayaku Co., Ltd.), etc.

[0124] 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.

[0125]

[0126] (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.)

[0127] 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.

[0128] The compounds shown in formulas (1-1) to (1-5) above can be synthesized by appropriately combining general methods of organic chemistry.

[0129] The reaction product of the polymer with epoxy groups on the side chain and the cinnamic acid derivative can be synthesized by reacting the polymer with the cinnamic acid derivative, as described above, preferably in the presence of a catalyst and preferably in a suitable organic solvent.

[0130] The proportion of cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 moles relative to 1 mole of epoxy groups contained in the epoxy-containing polymer, more preferably 0.05 to 1.3 moles, and even more preferably 0.1 to 1.1 moles.

[0131] As a catalyst that can be used here, an organic base or a compound known as a curing accelerator that promotes the reaction of epoxy compounds with acid anhydrides can be used.

[0132] 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.

[0133] 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; 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 octanoate, tin octanoate, 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.

[0134] 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.

[0135] 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.

[0136] 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 solubility of the raw materials and products, as well as 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).

[0137] 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.

[0138] 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 in the preparation of compositions for curing films.

[0139] Furthermore, in this embodiment, the acrylic copolymer of component (A) may also be a mixture of various specific copolymers.

[0140] 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.

[0141] [(B) Component]

[0142] The (B) component contained in the curing film forming composition of this embodiment is a polymer having structural units having N-hydroxymethyl or N-alkoxymethyl and structural units having partial structures shown in the above formula (1). More specifically, it is a polymer (hereinafter also referred to as specific copolymer 2) that copolymerizes monomers having N-alkoxymethyl or N-hydroxymethyl and monomers having groups shown in the above formula (1).

[0143] As a monomer having N-alkoxymethyl or N-hydroxymethyl, compounds such as those shown in formula (X1) below are preferred.

[0144]

[0145] (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)

[0146] Specific examples of the compounds shown in formula (X1) above include acrylamide compounds or methacrylamide compounds in which hydroxymethyl or alkoxymethyl groups are substituted, such as N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide. It should be noted that the term "(meth)acrylamide" refers to both methacrylamide and acrylamide.

[0147] 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.

[0148] 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.

[0149] Among them, methyl, ethyl, n-propyl, n-butyl and isobutyl are preferred.

[0150] 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.

[0151] 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-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy. Oxygen compounds, including 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.

[0152] Among them, methoxy, ethoxy and n-propoxy are preferred.

[0153] In the above formula (1), Q2 represents O, S or NQ3, and Q3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms represented by Q3 include groups having 1 to 4 carbon atoms among the specific examples of alkyl groups having 1 to 6 carbon atoms represented by Q1 above, preferably alkyl groups having 1 to 3 carbon atoms, and more preferably methyl groups.

[0154] Examples of monomers having the group shown in formula (1) include acetoacetoxyethyl acrylate and acetoacetoxyethyl methacrylate.

[0155] The amount of monomers having N-hydroxymethyl or N-alkoxymethyl and monomers having the groups shown in formula (1) used to obtain a polymer having structural units having N-hydroxymethyl or N-alkoxymethyl and structural units having partial structures shown in formula (1) is based on the total amount of all monomers used to obtain the specific copolymer 2. The monomers having N-hydroxymethyl or N-alkoxymethyl 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 groups 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%.

[0156] When obtaining a polymer having a structural unit having an N-hydroxymethyl or N-alkoxymethyl group and a structural unit shown in formula (1) above, a monomer having a non-reactive functional group, as exemplified in item (A) above, may be used. If the total amount of the monomer having an N-hydroxymethyl or N-alkoxymethyl group and the monomer having a group shown in formula (1) is less than 100 mol%, the amount of the monomer having a non-reactive functional group used is the remainder.

[0157] The weight-average molecular weight of the polymer (B) component of such a polymer 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 70,000.

[0158] These (B) components of polymers can be used alone or in combination of two or more.

[0159] The content of the polymer having structural units having N-hydroxymethyl or N-alkoxymethyl and structural units having partial structures as shown in the above formula (1) in the composition for forming the cured film of this embodiment is preferably 10 parts to 3000 parts by mass based on 100 parts by mass of the compound as component (A), more preferably 20 parts to 2500 parts by mass.

[0160] [(C) component]

[0161] In the curing film forming composition of this embodiment, an ammonium salt may be further included as component (C). By including the ammonium salt, the reaction for capturing formaldehyde can be promoted, thereby significantly reducing the amount of formaldehyde contained in the curing film forming composition. Examples of ammonium salts as component (C) include ammonium chloride, ammonium bromide, ammonium fluoride, ammonium iodide, ammonium acetate, ammonium carbonate, ammonium formate, ammonium phosphate, and ammonium borate, but ammonium acetate is preferred from the perspective of availability.

[0162] When the composition for forming a cured film in this embodiment contains an ammonium salt as component (C), its content is preferably 0.001 parts by mass to 100 parts by mass based on 100 parts by mass of the compound as component (A), and more preferably 0.01 parts by mass to 60 parts by mass.

[0163] [(D) component]

[0164] The curing film forming composition for forming the curing film on the surface of the optical film of the present invention, in addition to the above-mentioned components (A), (B) and (C) as needed, further contains a crosslinking catalyst as component (D).

[0165] 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 a cured film using a curing film forming composition that forms the surface of the optical film of the present invention.

[0166] 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, or a compound that thermally decomposes to produce an acid during pre-baking or post-baking, i.e., a compound that thermally decomposes to produce an acid at a temperature of 60°C to 250°C.

[0167] Examples of such compounds include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, 1,2-ethanedisulfonic acid, methanesulfonic anhydride, and other sulfonic acids or their hydrates and salts.

[0168] In addition, examples of compounds that produce acids by 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 shown in formulas [TAG-1] to [TAG-41] below.

[0169]

[0170] The above-mentioned ingredient (D) can be obtained as a commercially available product, for example, TA-100, TA-100FG, IK-1, IK-1FG (all manufactured by SunA Pro Co., Ltd.), SunAid (registered trademark) SI-B2A, SunAid (registered trademark) SI-B7, SunAid (registered trademark) SI-B3A, SunAid (registered trademark) SI-B3, etc. San-Aid (registered trademark) SI-B5, San-Aid (registered trademark) SI-B4, San-Aid (registered trademark) SI-150, San-Aid (registered trademark) SI-110, San-Aid (registered trademark) SI-60, San-Aid (registered trademark) SI-80, San-Aid (registered trademark) SI-100 (and above, manufactured by Sanshin Chemical Industry Co., Ltd.), etc.

[0171] The content of component (D) in the curable film forming composition of the present invention is 0.01 to 500 parts by mass relative to 100 parts by mass of the photo-alignment component (A), preferably 0.01 to 400 parts by mass, more preferably 0.05 to 300 parts by mass, and even more preferably 0.1 to 200 parts by mass. By making the content of component (D) 0.01 parts by mass or more, sufficient thermosetting and solvent resistance can be imparted, as well as high sensitivity to exposure. Furthermore, by making it 500 parts by mass or less, the curable film forming composition can have good storage stability.

[0172] [(E) component]

[0173] The composition for forming a cured film in this embodiment may contain a hydrophilic polymer as component (E).

[0174] Furthermore, the polymer that is component (E) can be a polymer having one or more substituents selected from hydroxyl, carboxyl and amino groups (hereinafter also referred to as a specific polymer).

[0175] In the composition for forming a cured film according to this embodiment, regarding the specific polymer as component (E), a highly hydrophilic polymer with high hydrophilicity compared to component (A) is preferably selected. Furthermore, the specific polymer is preferably a polymer having hydrophilic groups such as hydroxyl, carboxyl, and amino groups; specifically, a polymer having one or more substituents selected from hydroxyl, carboxyl, and amino groups is preferred.

[0176] Regarding polymers that are components (E), examples include acrylic polymers, urethane-modified acrylic polymers, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polyalkylimide, polyallylamine, cellulose (cellulose or its derivatives), phenolic varnish resin, melamine-formaldehyde resin, and other polymers with linear or branched structures, as well as cyclic polymers such as cyclodextrins.

[0177] Among them, as an acrylic polymer, it can be obtained by polymerizing monomers with unsaturated double bonds such as acrylates, methacrylates, and styrene.

[0178] Regarding the specific polymer used as component (E), preferred polymers include hydroxyalkyl cyclodextrins, cellulose polymers, acrylic polymers having at least one of polyethylene glycol ester groups and hydroxyalkyl ester groups having 2 to 5 carbon atoms, and at least one of carboxyl groups and phenolic hydroxyl groups, acrylic polymers with aminoalkyl side chains, acrylic polymers with hydroxyalkyl side chains such as polyhydroxyethyl methacrylate, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.

[0179] As a preferred example of a specific polymer as component (E), an acrylic polymer having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, and at least one of a carboxyl group and a phenolic hydroxyl group, is acceptable as long as it is an acrylic polymer having such a structure. There are no particular limitations on the backbone of the main chain of the polymer constituting the acrylic polymer and the type of side chains.

[0180] As a structural unit having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, the preferred structural unit is represented by the following formula [E1].

[0181] As a structural unit having at least one of a carboxyl group and a phenolic hydroxyl group, the preferred structural unit is represented by the following formula [E2].

[0182]

[0183] In the above equations [E1] and [E2], X 3 and X 4 Each can independently represent a hydrogen atom or a methyl group, Y 1 It represents H-(OCH2CH2) n -A hydroxyalkyl group (here, n is 2 to 50, preferably 2 to 10) or a hydroxyalkyl group having 2 to 5 carbon atoms, Y 2 This indicates a group that has a carboxyl group or a phenolic hydroxyl group.

[0184] The weight-average molecular weight of the acrylic polymer used as an example of component (E) is preferably 3,000 to 200,000, more preferably 4,000 to 150,000, and even more preferably 5,000 to 100,000. If the weight-average molecular weight exceeds 200,000 and is too large, the solubility in solvents may decrease, resulting in reduced workability. If the weight-average molecular weight is less than 3,000 and is too small, it may sometimes result in insufficient curing during thermosetting, leading to reduced solvent resistance and heat resistance. It should be noted that the weight-average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard material. The same applies below in this specification.

[0185] Regarding the synthesis method of acrylic polymers as an example of component (E), a simple method is to copolymerize a monomer having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms (hereinafter also referred to as e1 monomer.) with a monomer having at least one of a carboxyl group and a phenolic hydroxyl group (hereinafter also referred to as e2 monomer.).

[0186] Examples of monomers containing polyethylene glycol ester groups include H-(OCH2CH2). n -OH monoacrylate or monomethacrylate. The value of n is 2 to 50, preferably 2 to 10.

[0187] Examples of monomers having 2 to 5 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and N-hydroxyethylacrylamide.

[0188] Examples of monomers containing carboxyl groups include acrylic acid, methacrylic acid, and vinylbenzoic acid.

[0189] Examples of monomers having phenolic hydroxyl groups include p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene.

[0190] Furthermore, in this embodiment, when synthesizing an acrylic polymer as an example of component (E), monomers other than e1 and e2 monomers can be used, specifically monomers that do not have hydroxyl or carboxyl groups, as long as the effect of the present invention is not impaired.

[0191] Examples of such monomers include, for instance, acrylate compounds such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and tert-butyl acrylate; methacrylate compounds such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate; maleimide compounds such as N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; acrylamide compounds; acrylonitrile; maleic anhydride; styrene compounds; and vinyl compounds.

[0192] The amounts of e1 and e2 monomers used to obtain an acrylic polymer as an example of component (E) are preferably based on the total amount of all monomers used to obtain an acrylic polymer as component (E), with e1 monomer being 2 mol% to 95 mol% and e2 monomer being 5 mol% to 98 mol%.

[0193] When using a monomer having only a carboxyl group as the e2 monomer, it is preferable that the e1 monomer is 60 mol% to 95 mol% and the e2 monomer is 5 mol% to 40 mol% based on the total amount of all monomers used to obtain the acrylic polymer as component (E).

[0194] On the other hand, when using a monomer with only phenolic hydroxyl groups as the e2 monomer, it is preferable that the e1 monomer is 2 mol% to 80 mol% and the e2 monomer is 20 mol% to 98 mol%. If the e2 monomer is too small, the liquid crystal orientation is prone to become insufficient, and if it is too large, the compatibility with component (A) is prone to decrease.

[0195] The method for obtaining acrylic polymers as examples of component (E) is not particularly limited. For example, they can be obtained by polymerization at a temperature of 50°C to 110°C in a solvent in which e1 monomer, e2 monomer, monomers other than e1 monomer and e2 monomer as needed, and polymerization initiator coexist. In this case, the solvent used is not particularly limited as long as it can dissolve e1 monomer and e2 monomer, and monomers other than e1 monomer and e2 monomer and polymerization initiator as needed are not particularly limited. Specific examples are described in the section on <solvents> below.

[0196] Preferred examples of specific polymers as component (E) include acrylic polymers with aminoalkyl side chains, such as substances obtained by polymerizing aminoalkyl ester monomers such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate; or substances obtained by copolymerizing such aminoalkyl ester monomers with one or more monomers selected from the above-mentioned e1 monomer, the above-mentioned e2 monomer, and monomers other than these monomers, such as monomers that do not have hydroxyl or carboxyl groups.

[0197] A preferred example of a specific polymer as component (E) is an acrylic polymer with hydroxyalkyl side chains, such as a substance obtained by polymerizing hydroxyalkyl ester monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxypentyl acrylate, and hydroxypentyl methacrylate; or a substance obtained by copolymerizing such hydroxyalkyl ester monomers with one or more monomers selected from the above-mentioned e1 monomer, the above-mentioned e2 monomer, and monomers other than these monomers, such as monomers that have neither hydroxyl nor carboxyl groups.

[0198] The acrylic polymers obtained by the above method, as examples of component (E), are typically in a solution dissolved in a solvent.

[0199] Furthermore, the solution of the acrylic polymer (e.g., component (E)) obtained by the above method can be added to diethyl ether, water, etc., under stirring to allow it to redefine. After filtering / washing the precipitate, it is dried at room temperature or by heating under normal or reduced pressure to produce a powder of the acrylic polymer (e.g., component (E)). Through the above operation, the polymerization initiator and unreacted monomers coexisting with the acrylic polymer (e.g., component (E)) can be removed, resulting in a purified powder of the acrylic polymer (e.g., component (E)). If the purification is insufficient in one operation, the above operation can be repeated by redissolving the obtained powder in a solvent.

[0200] Examples of preferred polyether polyols as a specific polymer of component (E) include polyethylene glycol, polypropylene glycol, and propylene glycol. In addition, substances obtained by adding or condensing propylene oxide, polyethylene glycol, polypropylene glycol, etc., with polyols such as bisphenol A, triethylene glycol, and sorbitol can also be mentioned. Specific examples of polyether polyols include ADEKA's P series, G series, EDP series, BPX series, FC series, CM series, Nippon Oil's Uniols (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, G-750, Uniols (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, Nonion (registered trademark) LT-221, ST-221, OT-221, etc.

[0201] Regarding a preferred example of a specific polymer as component (E), a preferred example of a polyester polyol is a substance obtained by reacting glycols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, and polypropylene glycol with polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, terephthalic acid, and isophthalic acid. Specific examples of polyester polyols include DIC Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, and OD-X-252. 3. OD-X-2555, OD-X-2560, Kurare Polyols P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, Kawasaki Chemical Industries MAXIMOL RDK-133, RFK-505, SDK-145, RMK-342, etc.

[0202] Regarding a preferred example of a specific polymer as component (E), polycaprolactone polyols include substances obtained by ring-opening polymerization of ε-caprolactam using polyols such as trimethylolpropane and ethylene glycol as initiators. Specific examples of polycaprolactone polyols include DIC Polylight (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, Daicel Chemical Plaquesel (registered trademark) 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, and 320.

[0203] Regarding a preferred example of a specific polymer as component (E), a polycarbonate polyol can be described as a substance obtained by reacting diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc., with polyols such as trimethylolpropane and ethylene glycol. Specific examples of polycarbonate polyols include Daicel Chemical Products (registered trademark) CD205, CD205PL, CD210, CD220, C-590, C-1050, C-2050, C-2090, C-3090, etc.

[0204] Examples of preferred celluloses as a specific polymer of component (E) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl ethyl cellulose, and cellulose, with hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose being preferred.

[0205] Examples of preferred cyclodextrins as a specific polymer of component (E) include cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin; methylated cyclodextrins such as methyl-α-cyclodextrin, methyl-β-cyclodextrin, and methyl-γ-cyclodextrin; hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, and 2... Hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3-dihydroxypropyl-β-cyclodextrin, 2,3-dihydroxypropyl-γ-cyclodextrin, and other hydroxyalkyl cyclodextrins.

[0206] A preferred example of a phenolic varnish resin that is a specific polymer of component (E) is, for example, phenol-formaldehyde condensate.

[0207] In the curing film forming composition of this embodiment, the polymer of component (E) can be used in powder form or in solution form in which the refined powder is dissolved in the solvent described later.

[0208] Furthermore, in the composition for forming a cured film in this embodiment, the polymer of component (E) can be a mixture of polymers of various components (E).

[0209] When the resin composition for forming the phase difference element of the present invention contains component (E), the content of component (A) is 100 parts by mass of the photoorientation component, preferably 10 parts by mass to 1000 parts by mass, and more preferably 30 parts by mass to 500 parts by mass.

[0210] [(F)Component]

[0211] The curing film forming composition of the present invention may also contain a component that improves the adhesion of the formed curing film (hereinafter also referred to as an adhesion-improving component) as component (F).

[0212] As a bonding-enhancing component (F), in order to improve the adhesion between the alignment member and the layer of the polymeric liquid crystal obtained by the curing film forming composition of the present invention, the polymeric functional groups of the polymeric liquid crystal and the crosslinking reaction sites of the alignment member can be connected by covalent bonds. As a result, the phase retardation member of this embodiment, formed by laminating and curing the polymeric liquid crystal on the alignment member, can maintain strong adhesion even under high temperature and high humidity conditions, and can exhibit high durability against peeling and the like.

[0213] As component (F), monomers and polymers having groups and polymerizable groups selected from hydroxyl and N-alkoxymethyl groups are preferred.

[0214] Examples of such (F) 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.

[0215] As an example of component (F), hydroxyl-containing polyfunctional acrylates (hereinafter also referred to as hydroxyl-containing polyfunctional acrylates) can be cited.

[0216] Examples of hydroxyl-containing polyfunctional acrylates as ingredients (F) include, for example, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol pentaacrylate. Commercially available examples include KAYARAD PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

[0217] As an example of component (F), compounds having one acryloyl group and one or more hydroxyl groups can also be cited. Specifically, examples include 10-hydroxydecyl acrylate, 10-hydroxydecyl methacrylate, and 12-hydroxydodecyl methacrylate.

[0218] Furthermore, as a component of (F), a compound may be cited that has at least one polymerizable group containing a C=C double bond and at least one N-alkoxymethyl group in one molecule.

[0219] Examples of polymerizable groups containing C=C double bonds include acryloyl, methacryloyl, vinyl, allyl, and maleimide.

[0220] 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 compounds shown in the following formula (X1) are preferably examples.

[0221]

[0222] (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)

[0223] Specific examples of the compounds shown in formula (X1) above include acrylamide compounds or methacrylamide compounds in which hydroxymethyl or alkoxymethyl groups are substituted, such as N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide. It should be noted that the term "(meth)acrylamide" refers to both methacrylamide and acrylamide.

[0224] Other options for components (F) that include polymerizable groups containing C=C double bonds and N-alkoxymethyl groups are preferably, for example, the following compounds.

[0225]

[0226] In the embodiments of the present invention, the content of component (F) in the liquid crystal alignment agent is preferably 1 to 200 parts by mass relative to 100 parts by mass of the alignment component as component (A), and more preferably 5 to 150 parts by mass.

[0227] [Other additives]

[0228] Other additives may be included in the composition for forming the cured film according to embodiments of the present invention, provided that the effects of the present invention are not compromised.

[0229] 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.

[0230] 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-nitrofluorenone, 5-nitrodihydroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4-nitropione, 4-nitrobenzophenone, and 5-nitroindole, as nitrophenyl compounds, are particularly preferred.

[0231] These sensitizers are not specifically limited to the substances mentioned above. They can be used alone or in combination with two or more compounds.

[0232] 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 sufficiently obtained; if the proportion is too large, the transmittance of the cured film may be reduced or the coating may be rough.

[0233] Furthermore, as long as the effects of the present invention are not compromised, the composition for forming a cured film according to embodiments of the present invention may contain silane coupling agents, surfactants, rheology modifiers, pigments, dyes, preservation stabilizers, defoamers, antioxidants, etc., as other additives.

[0234] [Solvent]

[0235] The curing film forming composition of the embodiments 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 has the ability to dissolve component (A), component (B), component (D), component (C), component (E), component (F) as needed, and other additives.

[0236] 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.

[0237] Solvents are available as commercial products, and examples thereof include, for example, Neutron (registered trademark) PM, Neutron (registered trademark) MIP, and Neutronタノール (registered trademark) IPM, ネオエタノール (registered trademark) IPE, ネオエタノール (registered trademark) PHI, ネオエタノール ( Registered trademarks) MHI, PIP, PIP, PIP, HIMTE, PIP Trademark) PHM, Novotel (Registered Trademark) IPME, Novolu (Registered Trademark) P-7 (above, manufactured by Daishin Chemical Co., Ltd.), etc.

[0238] These solvents can be used alone or in combination of two or more. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, cyclohexanone, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate, and Neo-Etanol (registered trademark) IPM are preferred due to their good film-forming properties and high safety.

[0239] <Preparation of Compositions for Curing Films>

[0240] The composition forming the cured film on the surface of the optical film of the present invention, as described above, comprises a photo-orientation component as component (A), a polymer as component (B) having structural units having N-hydroxymethyl or N-alkoxymethyl and structural units having partial structures shown in formula (1) above, and a crosslinking catalyst as component (D) dissolved in a solvent. Furthermore, it may contain an ammonium salt as component (C), a hydrophilic polymer as component (E), and a binding enhancer as component (F), as needed. Moreover, other additives may be included as long as they do not impair the effects of the present invention.

[0241] Preferred examples of the resin composition for forming the phase difference element of the present invention are described below.

[0242] [1]: A resin composition for forming a phase difference element containing (A) a photoorientation component, (B) a component of 10 to 2000 parts by mass based on 100 parts by mass of (A) a component of (D) a crosslinking catalyst of 0.01 to 200 parts by mass relative to 100 parts by mass of (A) a component of (A).

[0243] [2]: A resin composition for forming a phase difference element containing (A) a photoorientation component, (B) component in the amount of 10 to 2000 parts by mass based on 100 parts by mass of (A), (C) ammonium salt in the amount of 0.001 to 100 parts by mass based on 100 parts by mass of (A), and (D) crosslinking catalyst in the amount of 0.01 to 200 parts by mass relative to 100 parts by mass of (A).

[0244] [3]: A resin composition for forming a phase difference element containing (A) a photoorientation component, (B) component (in the amount of 10 to 2000 parts by mass based on 100 parts by mass of (A), (C) ammonium salt (in the amount of 0.001 to 100 parts by mass based on 100 parts by mass of (A), (D) crosslinking catalyst (in the amount of 0.01 to 200 parts by mass relative to 100 parts by mass of (A), and (E) base polymer (in the amount of 10 to 1000 parts by mass based on 100 parts by mass of (A).

[0245] [3-2]: A resin composition for forming a phase difference element containing (A) a photoorientation component, (B) a component of 10 to 2000 parts by mass based on 100 parts by mass of (A), (D) a crosslinking catalyst of 0.01 to 200 parts by mass relative to 100 parts by mass of (A), and (E) a base polymer of 10 to 1000 parts by mass based on 100 parts by mass of (A).

[0246] [4]: A resin composition for forming a phase difference element containing (A) a photoorientation component, (B) a component of 10 to 2000 parts by mass based on 100 parts by mass of (A), (C) an ammonium salt of 0.001 to 100 parts by mass based on 100 parts by mass of (A), (D) a crosslinking catalyst of 0.01 to 200 parts by mass relative to 100 parts by mass of (A), and (F) a component of 1 to 200 parts by mass based on 100 parts by mass of (A).

[0247] [5]: A resin composition for forming a phase gradation element containing (A) a photoorientation component, (B) a component of 10 to 2000 parts by mass based on 100 parts by mass of (A), (C) an ammonium salt of 0.001 to 100 parts by mass based on 100 parts by mass of (A), (D) a crosslinking catalyst of 0.01 to 200 parts by mass relative to 100 parts by mass of (A), (E) a base polymer of 10 to 1000 parts by mass based on 100 parts by mass of (A), and (F) a component of 1 to 200 parts by mass based on 100 parts by mass of (A).

[0248] [5-2]: A resin composition for forming a phase difference element containing (A) a photoorientation component, (B) a component of 10 to 2000 parts by mass based on 100 parts by mass of (A), (D) a crosslinking catalyst of 0.01 to 200 parts by mass relative to 100 parts by mass of (A), (E) a base polymer of 10 to 1000 parts by mass based on 100 parts by mass of (A), and (F) a component of 1 to 200 parts by mass based on 100 parts by mass of (A).

[0249] The following details the mixing ratios, modulation methods, etc., when using the composition of the cured film forming the surface of the optical film of the present invention in solution form.

[0250] Regarding the proportion of solid components in the composition for forming the cured film on the surface of the optical film 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 composition for forming the cured film after the solvent has been removed.

[0251] The method for preparing the composition for forming the cured film on the surface of the optical film of the present invention is not particularly limited. Examples of preparation methods include, for instance, mixing component (A), component (C), component (D), and further components (E) and (F) as needed in a solution of component (B) dissolved in a solvent in a predetermined proportion to prepare a homogeneous solution, or mixing by adding other additives as needed at an appropriate stage of the preparation method.

[0252] In the preparation of the composition for forming the cured film on the surface of the optical film of the present invention, as described above, a solution of the specific copolymer 2 (component (B)) obtained by polymerization in a solvent can be used directly. In this case, for example, component (A), further component (C), further component (D), component (E), etc., are added to a solution of component (B) obtained by copolymerizing the monomer having N-hydroxymethyl or N-alkoxymethyl, the monomer having the group shown in formula (1), and other monomers as needed, to prepare a homogeneous solution. At this time, solvent may be added further for the purpose of concentration adjustment. At this time, the solvent used in the manufacturing process of component (B) may be the same as the solvent used for concentration adjustment of the composition for forming the cured film, or it may be different.

[0253] 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 the curing film.

[0254] <Curing film, alignment components and phase difference components>

[0255] 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 hot plate or an oven.

[0256] 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.

[0257] The thickness of the cured film on the surface of the optical film 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.

[0258] The optical film of the present invention, produced by such operation, can be irradiated with polarized UV light to make the cured film formed on the substrate a liquid crystal alignment film, that is, it can function as a component for aligning liquid crystal compounds, such as polymeric liquid crystals, and can be used as an alignment member.

[0259] As a method of irradiating polarized UV light, it is carried out by irradiating linearly polarized light from a vertical or oblique direction at room temperature or under heated conditions using ultraviolet to visible light with wavelengths of 150 nm to 450 nm.

[0260] In the alignment member of the present invention, the cured film, which serves as a liquid crystal alignment film, possesses solvent resistance and heat resistance. Therefore, after coating the alignment member with a phase retardation material composed of a polymeric liquid crystal solution, the material is heated to the phase transition temperature of the liquid crystal, thereby aligning the phase retardation material in a liquid crystal state on the alignment member. Furthermore, the phase retardation material, which has reached the desired alignment state, can be directly cured to form a phase retardation member having a layer with optical anisotropy.

[0261] As a phase difference 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 member is a film, the phase difference member of the present invention is useful as a phase difference film. The phase difference material forming such a phase difference member is in a liquid crystal state, and horizontal alignment, cholesterol-type alignment, vertical alignment, mixed alignment, etc., are formed on the alignment member, and can be used separately according to the desired phase difference characteristics.

[0262] Furthermore, in the case of manufacturing patterned retardation elements used in 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 angle, through a mask with a line and gap pattern. Then, after removing the mask, the film is exposed to polarized UV light at a -45-degree angle 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 element. Then, after coating the alignment element with a retardation material composed of a polymeric liquid crystal solution, it is heated to the phase transition temperature of the liquid crystal, thereby converting the retardation material into a liquid crystal state. The polymeric liquid crystal in the liquid crystal state aligns on the alignment element forming the two liquid crystal alignment regions, forming an alignment state corresponding to each liquid crystal alignment region. Furthermore, the retardation material achieving such an alignment state can be directly cured, fixing the aforementioned alignment state, resulting in multiple patterned retardation elements with two retardation regions of different retardation characteristics regularly arranged.

[0263] The optical film of the present invention can also be used as a liquid crystal alignment film for a liquid crystal display element. For example, the optical film of this embodiment, which is formed as described above, can be bonded together with the alignment members of the two optical films facing each other via spacers, and liquid crystal can be injected between these substrates to manufacture a liquid crystal aligned liquid crystal display element.

[0264] Therefore, the optical film of the present invention can be used to manufacture various phase retardation devices (phase retardation films), liquid crystal display elements, etc.

[0265] Example

[0266] The present invention will be specifically described below with examples of its embodiments, but the invention is not limited thereto.

[0267] [Abbreviations used in the embodiments]

[0268] The meanings of the abbreviations used in the following embodiments are as follows.

[0269] <Raw Materials>

[0270] BMAA: N-Butoxymethylacrylamide

[0271] AAEM: (2-acetylacetoxy)ethyl methacrylate (a monomer having the group shown in formula (1))

[0272] 4HBA: 4-Hydroxybutyl acrylate (equivalent to e1 monomer)

[0273] MMA: Methyl methacrylate (equivalent to e2 monomer)

[0274] AIBN: α,α'-azobisisobutyronitrile

[0275] MAIB: Dimethyl 2,2'-azobis(isobutyric acid)

[0276] <Component A>

[0277] MCA:

[0278] M6CA:

[0279] <Component C>

[0280] AcNH4: Ammonium acetate

[0281] <Component D: Crosslinking Catalyst>

[0282] PTSA: p-Toluenesulfonic acid Monohydrate

[0283] CSA: (±)-10-Camphorsulfonic acid

[0284] PPTS: Pyridine p-toluenesulfonate

[0285] <Component E>

[0286] PEPO: Polylite (registered trademark) 8651 (manufactured by DIC Corporation, polyester polyol)

[0287] RMK: Makishimor (registered trademark) RMK-342 (manufactured by Kawasaki Chemical Industry Co., Ltd., polyester polyol)

[0288] HPC: NISSO HPC-SSL (manufactured by Nippon Soda Co., Ltd., hydroxypropyl cellulose)

[0289] <F component>

[0290] HDC-DA:

[0291] 10HDA: 10-Hydroxydecyl Acrylate

[0292] 10HDMA: 10-Hydroxydecyl Methacrylate

[0293] 12HDDMA: 12-Hydroxydodecyl methacrylate

[0294] PET30: KAYARAD PET-30 (manufactured by Nippon Kayaku Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate)

[0295] <Other Additives>

[0296] MEK-ST-L: Organic silica sol MEK-ST-L (manufactured by Nissan Chemical Co., Ltd.) (30% by mass MEK dispersion)

[0297] <Solvent>

[0298] PM: Propylene glycol monomethyl ether

[0299] IPM: Neo-Eta Noru (registered trademark) IPM (manufactured by Daishin Chemical Co., Ltd.)

[0300] EA: Ethyl acetate

[0301] BA: Butyl acetate

[0302] CPN: Cyclopentanone

[0303] MEK: Methyl Ethyl Ketone

[0304] <Determination of weight-average molecular weight>

[0305] Device: GPC device (HLC-8320) manufactured by Toseo Co., Ltd.

[0306] Pillars: TSKgel (registered trademark) α-4000 and TSKgel (registered trademark) α-3000 manufactured by Higashi Sou Co., Ltd.

[0307] Column oven: 40℃

[0308] Flow rate: 1 mL / min

[0309] Eluent: N,N-dimethylformamide

[0310] Standard sample: Polystyrene

[0311] <Synthesis of Component B>

[0312] <Synthesis example 1>

[0313] After dissolving BMAA (50.0 g, 318 mmol), AAEM (3.58 g, 16.7 mmol), α-thioglycerol (0.362 g, 3.35 mmol) as a chain transfer agent, and MAIB (0.154 g, 0.669 mmol) as a polymerization catalyst in PM (36.0 g), the solution was added dropwise over 60 minutes while PM (90.1 g) was maintained at 70 °C. After the addition was complete, the reaction was allowed to proceed overnight, yielding a solution (PB-1) of an acrylic copolymer (BMAA / AAEM = 95 / 5 molar ratio) (solids concentration 30% by mass). The weight-average molecular weight (Mw) of the obtained acrylic copolymer was 26,000.

[0314] <Synthesis example 2>

[0315] After dissolving BMAA (47.0 g, 299 mmol), AAEM (7.11 g, 33.2 mmol), α-thioglycerol (0.359 g, 3.32 mmol) as a chain transfer agent, and MAIB (0.153 g, 0.664 mmol) as a polymerization catalyst in PM (36.4 g), the solution was added dropwise over 60 minutes while PM (91.0 g) was maintained at 70 °C. After the addition was complete, the reaction was allowed to proceed overnight, yielding a solution (PB-2) of an acrylic copolymer (BMAA / AAEM = 90 / 10 molar ratio) (solids concentration 30% by mass). The weight-average molecular weight (Mw) of the obtained acrylic copolymer was 52,300.

[0316] <Synthesis Example 3>

[0317] After dissolving BMAA (34.0 g, 216 mmol), AAEM (19.8 g, 92.4 mmol), α-thioglycerol (0.334 g, 3.09 mmol) as a chain transfer agent, and MAIB (0.142 g, 0.617 mmol) as a polymerization catalyst in PM (36.2 g), the solution was added dropwise over 60 minutes while PM (90.5 g) was maintained at 70 °C. After the addition was complete, the reaction was allowed to proceed overnight, yielding a solution (PB-3) of an acrylic copolymer (BMAA / AAEM = 70 / 30 molar ratio) (solids concentration 30% by mass). The weight-average molecular weight (Mw) of the obtained acrylic copolymer was 56,000.

[0318] <Synthesis example 4>

[0319] After dissolving BMAA (23.0 g, 146 mmol), AAEM (31.3 g, 146 mmol), α-thioglycerol (0.316 g, 2.92 mmol) as a chain transfer agent, and MAIB (0.134 g, 0.582 mmol) as a polymerization catalyst in PM (36.5 g), the solution was added dropwise over 60 minutes while PM (91.3 g) was maintained at 70 °C. After the addition was complete, the reaction was allowed to proceed overnight, yielding a solution (PB-4) of an acrylic copolymer (BMAA / AAEM = 50 / 50 molar ratio) (solids concentration 30% by mass). The weight-average molecular weight (Mw) of the obtained acrylic copolymer was 60,000.

[0320] <Synthesis of component E>

[0321] <Synthesis example 5>

[0322] After dissolving 4HBA (197.0 g, 1.37 mol) and MAIB (3.1 g, 13 mmol) as a polymerization catalyst in PM (133.4 g), the solution was added dropwise over 2 hours while PM (166.8 g) was 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 (PE-1) (solids concentration 40% by mass). The weight-average molecular weight (Mw) of the obtained acrylic polymer was 22,700.

[0323] <Synthesis Example 6>

[0324] After dissolving 4HBA (248.0 g, 1.72 mol), α-thioglycerol (1.9 g, 18 mmol), and MAIB (0.20 g, 0.87 mmol) as a polymerization catalyst in PM (166.7 g), the solution was added dropwise over 4 hours while PM (83.4 g) was maintained at 70 °C. After the addition was complete, the reaction was allowed to proceed for 18 hours to obtain a solution of acrylic polymer (PE-2) (50% by mass solids). The weight-average molecular weight (Mw) of the obtained acrylic polymer was 24,000.

[0325] <Synthesis Example 7>

[0326] After dissolving MMA (84.4 g, 843 mmol), 4HBA (13.5 g, 93.6 mmol), and MAIB (2.2 g, 9.6 mmol) as a polymerization catalyst in PM (150.1 g), the solution was added dropwise over 2 hours while PM (250.2 g) was maintained at 70 °C. After the addition was complete, the reaction was allowed to proceed for 18 hours to obtain a solution (PE-3) of an acrylic copolymer (MMA / 4HBA = 90 / 10 molar ratio) (solids concentration 20% by mass). The weight-average molecular weight (Mw) of the obtained acrylic copolymer was 38,900.

[0327] <Synthesis of Other Additives>

[0328] <Synthesis example 8>

[0329] After dissolving BMAA (145.5 g, 925.5 mmol) and AIBN (4.6 g, 28 mmol) as a polymerization catalyst in PM (150.1 g), the solution was added dropwise over 30 minutes while maintaining PM (200.1 g) at 80 °C. After the addition was complete, the reaction was allowed to proceed for 5 hours to obtain a solution of the acrylic polymer (PBMAA) (solids concentration 30% by mass). The weight-average molecular weight (Mw) of the obtained acrylic polymer was 23,000.

[0330] <Modulation Example 1>

[0331] PEPO (100 parts by mass) as component (E), MCA (30 parts by mass) as component (A), and PB-1 (190 parts by mass) obtained in Synthesis Example 1 as component (B) were mixed. PM as a solvent was added and the mixture was stirred for 2 hours. Dissolution was confirmed by visual inspection, and a solution was obtained. 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.

[0332] <Modulation Examples 2-15, 17-18, 20-41, 43>

[0333] Using the ingredients of the types and mixing amounts shown in Table 1 below, except that the same operation was performed as in Modification Example 1, (A-2)~(A-15), (A-17)~(A-18), (A-20)~(A-34), (B-1)~(B-7), and (B-9) were prepared.

[0334] <Modulation Example 16>

[0335] PE-2 (100 parts by mass) obtained in Synthesis Example 7 as component (E), PE-3 (40 parts by mass) obtained in Synthesis Example 8, M6CA (40 parts by mass) as component (A), PB-1 (174 parts by mass) obtained in Synthesis Example 1 as component (B), AcNH4 (1 part by mass) as component (C), 10HDA (8 parts by mass) as component (F), and MEK-ST-L (40 parts by mass) as additive were mixed. A solvent was added to form PM and MEK with a mass ratio of PM:MEK = 97.75:2.05, and the mixture was stirred for 2 hours. Dissolution was confirmed by visual inspection, and a solution was obtained. The obtained solution was then filtered through a glass filter with a pore size of 1.0 μm to prepare a composition (A-16) with a solid content concentration of 8.0% by mass.

[0336] <Modulation Examples 19, 42>

[0337] Using the types and mixing amounts of each component shown in Table 1 below, except that the operation was the same as in Modification Example 16, (A-19) and (B-8) were prepared.

[0338] [Table 1]

[0339] [Quantitative determination of formaldehyde concentration in the composition]

[0340] <Example 1>

[0341] Formaldehyde in the composition was detected by derivatization using the acetylacetone method. The acetylacetone method is a method of labeling by mixing the sample solution with the reaction solution according to the reaction of Formula 1 below. In this example, following the general procedure of the acetylacetone method, a reaction solution was used, consisting of 15 g of ammonium acetate, 600 μL of acetic acid, and 500 μL of acetylacetone diluted to 200 mL with MilliQ ultrapure water. As a pretreatment, 700 μL of pure water was added to a microtube, followed by 300 μL of A-1 prepared in Preparation Example 1. The mixture was stirred with a stirring rotor for 2 minutes, and then centrifuged to recover the supernatant. 700 μL of the reaction solution and 300 μL of the supernatant were added, and the mixture was reacted at 50°C for 30 minutes, then allowed to stand at room temperature for 30 minutes to prepare a formaldehyde derivatized solution diluted 11.1 times. The modified solution was used to quantify the formaldehyde derivatives in the formaldehyde derivative solution as derivatives of the compound by liquid chromatography. The result showed that the formaldehyde concentration in A-1 was 1.5 ppm.

[0342]

[0343] <Examples 2-34>

[0344] The procedure was the same as in Example 1, except that A-1 was changed to A-2 to A-34, and the formaldehyde concentration was quantified. The results are shown in Table 2 below.

[0345] <Comparative Examples 1-9>

[0346] The procedure was the same as in Example 1, except that A-1 was changed to B-1 to B-9, and the formaldehyde concentration was quantified. The results are shown in Table 2 below.

[0347] [Table 2]

[0348] The results in Table 2 clearly show that the amount of formaldehyde can be significantly reduced by copolymerizing monomers having the group shown in Formula (1) with monomers having N-hydroxymethyl or N-alkoxymethyl groups.

[0349] <Preparation of Catalyst Solution>

[0350] <Modulation Example 44>

[0351] PTSA (1.0 g) as a catalyst and PM (19.0 g) as a solvent were added and stirred for 1 hour to confirm dissolution by visual inspection. The solution was then filtered through a 0.2 μm filter to prepare the catalyst solution (D-1).

[0352] <Modulation Example 45>

[0353] PPTS (1.0 g) as a catalyst and PM (19.0 g) as a solvent were added and stirred for 1 hour to confirm dissolution by visual inspection. The solution was then filtered through a 0.2 μm filter to prepare the catalyst solution (D-2).

[0354] <Modulation Example 46>

[0355] CSA (2.0 g) as a catalyst and PM (18.0 g) as a solvent were added and stirred for 1 hour to confirm dissolution by visual inspection. The solution was then filtered through a 0.2 μm filter to prepare the catalyst solution (D-3).

[0356] <Modulation of Liquid Crystal Alignment Agent>

[0357] <Example 35>

[0358] In the A-1 (2.00 g) obtained in Modulation Example 1, D-1 (0.12 g) obtained in Modulation Example 44 and EA (0.54 g) as a diluent were added and stirred for 1 minute to obtain the liquid crystal alignment agent AL-1.

[0359] <Examples 36-45, 52, 55-62>

[0360] The same procedure was followed as in Example 35, but A-1 was changed to A-2 to 11, A-18, and A-21 to A-28 to obtain liquid crystal alignment agents AL-2 to 11, AL-18, and AL-21 to 28. The mixing amounts of the components, etc., are shown in Table 3.

[0361] <Comparative Examples 10-15>

[0362] The same procedure was followed as in Example 35, but A-1 was changed to B-1 to B-6, resulting in liquid crystal alignment agents BL-1 to B-6. The mixing amounts of the components, etc., are shown in Table 3.

[0363] <Example 46>

[0364] To A-12 (2.00 g) obtained in Modulation Example 12, D-2 (0.12 g) obtained in Modulation Example 45 and EA (0.54 g) as a diluent were added, and the mixture was stirred for 1 minute to obtain liquid crystal alignment agent AL-12. The mixing amounts of the components, etc., are shown in Table 3.

[0365] <Examples 47-49>

[0366] The same procedure was followed as in Example 46, but A-12 was changed to A-13 to A-15 to obtain liquid crystal alignment agents AL-13 to A-15. The mixing amounts of the components, etc., are shown in Table 3.

[0367] <Comparative Example 16>

[0368] The procedure was the same as in Example 46, except that A-12 was replaced with B-7, resulting in liquid crystal alignment agent BL-7. The mixing amounts of the components, etc., are shown in Table 3.

[0369] <Example 50>

[0370] To A-16 (2.00 g) obtained in Modulation Example 16, D-3 (0.08 g) obtained in Modulation Example 46 and EA (0.5 g) and IPM (1.3 g) as diluents were added, and the mixture was stirred for 24 hours to obtain liquid crystal alignment agent AL-16. The mixing amounts of the components are shown in Table 3.

[0371] <Examples 51, 53-54, 63-68>

[0372] The same procedure was followed as in Example 50, but A-16 was changed to A-17, A-19 to 20, and A-29 to 34 to obtain liquid crystal alignment agents AL-17, AL-19 to 20, and AL-29 to 34. The mixing amounts of the components, etc., are shown in Table 3.

[0373] <Comparative Examples 17-18>

[0374] The same procedure was followed as in Example 50, except that A-16 was replaced with B-8 and B-9, resulting in liquid crystal alignment agents BL-8 and BL-9. The mixing amounts of the components, etc., are shown in Table 3.

[0375] [Table 3]

[0376] <Preparation of Polymerizable Liquid Crystal Solution for Horizontal Orientation>

[0377] Paliocolor LC-242 (manufactured by BASF Japan Co., Ltd.) (19.3g) was added as a polymerizable liquid crystal for horizontal alignment; Omnirad 907 (manufactured by IGM Resins BV) (0.6g) was added as a photoradical initiator; and BYK-361N (Bick) was added as a leveling agent. Kemijapan (manufactured by Co., Ltd.) (0.1g), further added CPN (80g) as a solvent, stirred for 2 hours, and confirmed by visual inspection that it dissolved, to obtain a 20% by mass polymeric liquid crystal solution (LC-1).

[0378] <Formation of Liquid Crystal Alignment Films and Fabrication of Phase Retardation Films>

[0379] <Example 69>

[0380] The liquid crystal alignment agent (AL-1) obtained in Example 35 was applied to the TAC film, which served as the substrate, using a rod coater to achieve a wet film thickness of 4 μm. The film was then heated and dried at 120°C for 1 minute in a hot air circulating oven, forming a cured film. Next, a heat treatment of 10 mJ / cm² was applied to the surface of the cured film. 2 A liquid crystal alignment film was formed by vertically irradiating linearly polarized light with a wavelength of 313 nm. A horizontally aligned polymerizable liquid crystal solution RMS16-089 (manufactured by Merck) was then applied to the liquid crystal alignment film using a rod coater to a wet film thickness of 12 μm. Following this, the film was heat-dried in an oven at 72°C for 1 minute, and then subjected to nitrogen atmosphere at 500 mJ / cm². 2 The exposure amount is vertically irradiated with unpolarized light of wavelength 365nm to solidify the polymeric liquid crystal and produce a phase retardation film.

[0381] <Examples 70-78, 86, Comparative Examples 19-23>

[0382] Using (AL-2) to (AL-10), (AL-18), and (BL-1) to (BL-5) as liquid crystal alignment agents, a phase retardation film was fabricated using the same operation as in Example 69.

[0383] <Example 79>

[0384] The liquid crystal alignment agent (AL-11) obtained in Example 45 was applied to the TAC film, which served as the substrate, using a rod coater to achieve a wet film thickness of 4 μm. The film was then heated and dried at 120°C for 2 minutes in a hot air circulating oven, forming a cured film. Next, a heat treatment of 20 mJ / cm² was applied to the surface of the cured film. 2 A liquid crystal alignment film was formed by vertically irradiating linearly polarized light with a wavelength of 313 nm. A horizontally aligned polymerizable liquid crystal solution LC-1 was then coated onto the liquid crystal alignment film using a rod coater to achieve a wet film thickness of 10 μm. Following this, the film was heated and dried in an oven at 100°C for 2 minutes, and then subjected to nitrogen atmosphere and a heat treatment rate of 400 mJ / cm². 2 The exposure amount is vertically irradiated with unpolarized light of wavelength 365nm to solidify the polymeric liquid crystal and produce a phase retardation film.

[0385] <Examples 80-83, 89-96, Comparative Examples 24-25>

[0386] Using (AL-12)~(AL-15), (AL-21)~(AL-28), and (BL-6)~(BL-7) as liquid crystal alignment agents, a phase retardation film was fabricated using the same operation as in Example 79.

[0387] <Example 84>

[0388] The liquid crystal alignment agent (AL-16) obtained in Example 50 was applied to an acrylic film serving as a substrate using a rod coater to achieve a wet film thickness of 10 μm. The film was then heated and dried at 90°C for 1 minute in a hot air circulating oven to form a cured film. Next, a heat treatment of 20 mJ / cm² was applied to the surface of the cured film. 2 A liquid crystal alignment film was formed by vertically irradiating linearly polarized light with a wavelength of 313 nm. A horizontally aligned polymerizable liquid crystal solution LC-1 was then applied to the liquid crystal alignment film using a rod coater to achieve a wet film thickness of 8 μm. Following this, the film was heated and dried in an oven at 90°C for 1 minute, and then subjected to nitrogen atmosphere and a heat treatment rate of 500 mJ / cm². 2 The exposure amount is vertically irradiated with unpolarized light of wavelength 365nm to solidify the polymeric liquid crystal and produce a phase retardation film.

[0389] <Examples 85, 87-88, 97-102, Comparative Examples 26-27>

[0390] Using (AL-17), (AL-19)~(AL-20), (AL-29)~(AL-34), and (BL-8)~(BL-9) as liquid crystal alignment agents, a phase retardation film was fabricated using the same operation as in Example 84.

[0391] The phase difference films fabricated above were evaluated using the methods described below. The evaluation results are shown in Table 4.

[0392] [Evaluation of Orientation]

[0393] The phase difference film on the fabricated substrate was sandwiched between a pair of polarizing plates, and the phase difference characteristics under the cross prism were observed visually. Cases where the phase difference was defect-free were marked as "○", and cases where the phase difference was not observed were marked as "×" and recorded in the "Orientation" column.

[0394] [Evaluation of fit]

[0395] On the surface of the phase retardation film (the surface on which the polymeric liquid crystal layer forms) of the fabricated substrate, squares (1mm × 1mm × 100 squares) were cut using a cutter. Then, celluloid tape (Nichiban Corporation cel tape (registered trademark), 24mm wide) was attached. Next, when the celluloid tape was peeled off, the number of squares that remained on the underlying cured film and the further lower film substrate without peeling off the overlapped polymeric liquid crystal layer was counted. Cases where all remained were marked as "○", cases where some were peeled off were marked as "△", and cases where all were peeled off were marked as "×", and these were recorded in the "Adhesion" column.

[0396] [Table 4]

[0397] The results in Table 4 clearly confirm that, regarding orientation and adhesion properties, even copolymerizing monomers with the groups shown in Formula (1) with monomers with N-hydroxymethyl or N-alkoxymethyl groups does not deteriorate the properties and only reduces the formaldehyde concentration.

Claims

1. A composition for forming a cured film, comprising: (A) Components: Compounds with photooriented groups; (B) Components: a polymer having: structural units having N-hydroxymethyl or N-alkoxymethyl, and structural units having a partial structure as shown in formula (1); and (D) Component: Crosslinking catalyst, 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.

2. The composition for forming a cured film according to claim 1, wherein the photooriented group of component (A) is a functional group that undergoes photodimerization or photoisomerization.

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

4. The composition for forming a cured film according to claim 1, wherein 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, further comprising an ammonium salt as component (C).

6. The composition for forming a cured film according to claim 5, wherein the ammonium salt of component (C) is ammonium acetate.

7. An orientation member obtained using the curing film forming composition according to any one of claims 1 to 6.

8. A phase difference element formed using a cured film obtained from the curing film forming composition according to any one of claims 1 to 6.

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