Resin composition for thermosetting photo-alignment film

Abstract

[Problem] To provide a composition capable of obtaining an alignment material having excellent alignment properties and heat resistance through firing at a low temperature in a short time without using a crosslinking agent containing an N-methylol group, an N-alkoxymethyl group, or the like. [Solution] This cured film-forming composition comprises (A) a compound represented by formula (a), (B) a polymer having an epoxy group, and (C) a thermal acid generator.

Description

Resin composition for thermosetting photo-alignment film

[0001] The present invention relates to a thermosetting resin composition for a photoalignment film (also referred to as a composition for forming a cured film), an alignment material, and a retardation material.

[0002] In a 3D display using circularly polarized glasses, a retarder is usually placed on a display element that forms an image, such as a liquid crystal panel. The retarder used for this purpose has a patterned configuration in which two types of retardation regions with different retardation properties are regularly arranged in multiple numbers. In the following description, such a retarder patterned to arrange multiple retardation regions with different retardation properties is referred to as a patterned retarder.

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

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

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

[0006] In recent years, liquid crystal materials applicable to this retardation plate (retardation layer) have been proposed that have reverse dispersion characteristics (Patent Documents 3 and 4). By using such liquid crystal materials with reverse dispersion characteristics, it is possible to ensure reverse dispersion characteristics by forming the retardation layer from a single layer, instead of forming a quarter-wave retardation plate from a two-layer retardation layer that combines a conventional half-wave plate and a quarter-wave plate, and thereby realize an optical film that can ensure a desired retardation over a wide wavelength band with a simple configuration.

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

[0008] Acrylic resins and polyimide resins having photodimerization moieties such as cinnamoyl groups and chalcone groups in their side chains are known as photoalignment materials that can be used in forming alignment materials using photoalignment methods. These resins have been reported to exhibit the ability to control the alignment of liquid crystals (hereinafter referred to as liquid crystal alignment property (liquid crystal alignment ability)) when irradiated with polarized UV light (see Patent Documents 5 to 7).

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

[0010] Incidentally, Patent Document 10 describes a thermosetting liquid crystal alignment material using a resin composition containing a compound having an N-methylol group or an N-alkoxymethyl group as a highly sensitive photoalignment agent.

[0011] However, compounds containing N-methylol groups are obtained by forming N-methylol groups through the reaction of amino groups with formaldehyde, and therefore, in principle, often contain trace amounts of formaldehyde. As of April 2023, formaldehyde is designated as a deleterious substance under the Poisonous and Deleterious Substances Control Act and is highly toxic to living organisms. It has also been shown by the International Agency for Research on Cancer to be carcinogenic. Furthermore, formaldehyde is released into the air from compounds used in building materials and furniture, causing sick building syndrome, which has become a problem. Therefore, when using compounds containing at least one of an N-methylol group and an N-alkoxymethyl group in products, it is necessary to reduce the formaldehyde concentration in the composition and, particularly in the case of molded products and paints, to ensure the safety of manufacturers and consumers who use the products.

[0012] Japanese Patent Application Laid-Open No. 2005-49865 Japanese Patent Application Laid-Open No. 10-68816 U.S. Patent No. 8,119,026 Specification Japanese Patent Application Laid-Open No. 2009-179563 Japanese Patent No. 3,611,342 Japanese Patent Application Laid-Open No. 2009-058584 Japanese Patent Publication No. 2001-517719 International Publication No. 2011 / 126022 International Publication No. 2014 / 010688 International Publication No. 2010 / 150748

[0013] When a thermal crosslinking system is introduced into a cured film, there is a concern about the generation of formaldehyde in cured film formation systems using crosslinking agents containing N-methylol groups, N-alkoxymethyl groups, etc. Therefore, there is a demand for a composition that can be used to obtain an alignment material with excellent alignment properties and heat resistance by baking at a low temperature and for a short time using a thermal crosslinking system that does not involve the risk of generating formaldehyde.

[0014] The present invention has been made based on the above findings and investigations, and an object of the present invention is to provide a cured film-forming composition that does not generate formaldehyde.

[0015] As a result of extensive research to achieve the above-mentioned objective, the inventors discovered that by using a composition containing a polymer having an epoxy group and a thermal acid generator as a photo-alignment component, an alignment material with excellent alignment properties and heat resistance can be obtained by baking at a low temperature for a short time without the risk of formaldehyde generation, and thus completed the present invention, which has the following gist.

[0016] That is, the present invention includes the following: [1] A composition for forming a cured film, comprising: (A) a compound represented by the following formula (a), (B) a polymer having an epoxy group, and (C) a thermal acid generator: [In the formula, A １ and A ２ each independently represents a hydrogen atom, a methyl group, or a cyano group. １ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, a di(alkyl)amino group having 1 to 6 carbon atoms, an OH group, or an NH ２ a group, a carboxy group, a trialkoxysilyl group, a cyano group, a nitro group, or a group represented by the following formula (c-1): (In formula (c-1), the dashed line represents Q ２ represents a bond with １０１ is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of this alkylene group may be replaced by a fluorine atom or an organic group. １０１ -CH in ２ CH ２ - may be replaced by -CH=CH-, and further, when any of the following groups are not adjacent to each other, the alkylene group may be interrupted by a group selected from the group consisting of -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO-, and M １ represents a hydrogen atom or a methyl group; ２ represents a single bond or an alkylene group having 1 to 20 carbon atoms, which may be branched or linear; Q ３represents a single bond, —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, or —CO—, with the proviso that Q ２ If is a single bond, Q ３ is also a single bond, and Q ４ represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused ring group; Q ５ represents a single bond, an oxygen atom, —CO—, —COO—, or —OCO—; q1 is an integer of 0 to 3; q2 is 0 or 1; and Q ６ represents a single bond, an oxygen atom or a sulfur atom; ７ represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear, and Q ６ When Q is a single bond, ７ is a single bond, and Q ８ is an OH group, NH ２ Q represents a hydroxyphenoxy group, a carboxyphenoxy group, an aminophenoxy group, an aminocarbonylphenoxy group, a phenylamino group, a hydroxyphenylamino group, a carboxyphenylamino group, an aminophenylamino group, a hydroxyalkylamino group, a bis(hydroxyalkyl)amino group, an alkoxysilyl group, a cyanophenylamino group, an alkoxy group having 1 to 12 carbon atoms, a haloalkoxy group having 1 to 12 carbon atoms, a cycloalkoxy group having 3 to 12 carbon atoms, a phenoxy group, or a biphenyloxy group, ２ , Q ３ , Q ６ and Q ７ are both single bonds, q1 is 0, and Q ８ When Q is an OH group, １represents a group other than a hydrogen atom as defined above.] [2] The cured film-forming composition according to the above [1], wherein q2 is 0. [3] The cured film-forming composition according to the above [1], wherein the polymer having an epoxy group, component (B), is a homopolymer of a polymerizable unsaturated compound having an epoxy group, or a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound. [4] The cured film-forming composition according to the above [1], wherein the thermal acid generator, component (C), is a sulfonium salt. [5] An alignment material obtained using the cured film-forming composition according to any one of the above [1] to [4]. [6] A retardation material formed using a cured film obtained from the cured film-forming composition according to any one of the above [1] to [4]. [7] A compound represented by the following formula (a): [In the formula, A １ and A ２ each independently represents a hydrogen atom, a methyl group, or a cyano group; A １ and A ２ At least one of Q represents a methyl group. １ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, or an OH group; Q ２ represents a single bond or an alkylene group having 1 to 20 carbon atoms, which may be branched or linear; Q ３ represents a single bond or —O—, provided that Q ２ If is a single bond, Q ３ is also a single bond, q1 is 0, q2 is 0, and Q ６ represents an oxygen atom, and Q ７ represents a methylene group or a group represented by the following formula (c-2): (In the formula, * represents a bond.) Q ８ represents an alkoxy group having 1 to 12 carbon atoms, a haloalkoxy group having 1 to 12 carbon atoms, a phenoxy group, a biphenyloxy group, or a cyclohexyloxy group.] [8] A compound represented by the following formula:

[0017] According to the present invention, an alignment material having excellent alignment properties and heat resistance can be obtained by baking at a low temperature for a short time without using a crosslinking agent containing an N-methylol group or an N-alkoxymethyl group, which may generate formaldehyde. Furthermore, according to the present invention, a retardation material can be obtained by directly curing the retardation material oriented on the alignment material, and also by transferring the oriented and cured retardation material to another substrate.

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

[0019] <Composition for forming a cured film> The composition for forming a cured film of the present invention is a composition for forming a cured film, which contains (A) the compound represented by (a) above (a compound having a photoalignable group), (B) a polymer having an epoxy group, and (C) a thermal acid generator. Each component will be described in detail below.

[0020] [Component (A)] The component (A) in the cured film-forming composition of the present invention is a compound represented by the above formula (a), and this compound has a photo-aligning group (such as a cinnamoyl structure or a naphthyl (meth)acryloyl structure in formula (a)), and preferably further has a thermally crosslinkable group (such as a hydroxy group, a carboxy group, an amide group, an amino group, or an alkoxysilyl group). It can be said to be a low molecular weight compound. Note that a portion of the light-aligning group may form a portion of the carboxy group or amide group listed as the thermally crosslinkable group, and the thermally crosslinkable group may be protected by a protecting group (such as an alkoxymethyl group or a trialkylsilyl group). In other words, the component (A) is a component that imparts photo-alignment properties to the cured film obtained from the cured film-forming composition of the present invention. In this specification, the component (A) is also referred to as a photo-alignment component.

[0021] The compound serving as component (A) is Q １is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, a di(alkyl group having 1 to 6 carbon atoms)amino group, or an OH group; Q ２ and Q ３ is a single bond, q1 is 0, q2 is 0, and Q ６ and Q ７ is a single bond, and Q ８ is preferably a compound (a-1) in which is an OH group.

[0022] Examples of such compounds (a-1) include ferulic acid, 4-methoxycinnamic acid, 4-propoxycinnamic acid, 4-cyclohexylcinnamic acid, and 4-(N,N-dimethylamino)cinnamic acid.

[0023] The compound serving as component (A) is Q １ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, or an OH group, and Q ２ and Q ３ is a single bond, q1 is 0, q2 is 0, and Q ６ and Q ７ is a single bond, and Q ８ NH ２ Compound (a-2) which is a group is preferred.

[0024] Examples of such compounds (a-2) include 4-methylcinnamic acid amide, 4-ethylcinnamic acid amide, 4-methoxycinnamic acid amide, and 4-ethoxycinnamic acid amide.

[0025] The compound serving as component (A) is Q １ is an OH group, and Q ２ is a single bond or an alkylene group having 1 to 20 carbon atoms, and Q ３ is a single bond, —O—, —COO— or —OCO—, q1 is 0, q2 is 0, and Q ６ and Q ７ is a single bond, and Q ８Also preferred is a compound (a-3) in which is an alkoxy group having 1 to 12 carbon atoms, a haloalkoxy group having 1 to 12 carbon atoms, a phenoxy group or a biphenyloxy group.

[0026] Specific examples of compound (a-3) include 4-(8-hydroxyoctyloxy)cinnamic acid methyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid methyl ester, 4-(4-hydroxybutyloxy)cinnamic acid methyl ester, 4-(3-hydroxypropyloxy)cinnamic acid methyl ester, 4-(2-hydroxyethyloxy)cinnamic acid methyl ester, 4-hydroxymethyloxycinnamic acid methyl ester, 4-hydroxycinnamic acid methyl ester, 4-(8-hydroxyoctyloxy)cinnamic acid ethyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid ethyl ester, 4-(4-hydroxybutyloxy)cinnamic acid ethyl ester, 4-(3-hydroxypropyloxy)cinnamic acid ethyl ester, 4-(2-hydroxyethyloxy)cinnamic acid ethyl ester, 4-hydroxymethyloxycinnamic acid ethyl ester, 4-hydroxycinnamic acid ethyl ester, 4-( Examples of the cinnamic acid phenyl ester include 4-(8-hydroxyoctyloxy)cinnamic acid phenyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid phenyl ester, 4-(4-hydroxybutyloxy)cinnamic acid phenyl ester, 4-(3-hydroxypropyloxy)cinnamic acid phenyl ester, 4-(2-hydroxyethyloxy)cinnamic acid phenyl ester, 4-hydroxymethyloxycinnamic acid phenyl ester, 4-hydroxycinnamic acid phenyl ester, 4-(8-hydroxyoctyloxy)cinnamic acid biphenyl ester, 4-(6-hydroxyhexyloxy)cinnamic acid biphenyl ester, 4-(4-hydroxybutyloxy)cinnamic acid biphenyl ester, 4-(3-hydroxypropyloxy)cinnamic acid biphenyl ester, 4-(2-hydroxyethyloxy)cinnamic acid biphenyl ester, 4-hydroxymethyloxycinnamic acid biphenyl ester, and 4-hydroxycinnamic acid biphenyl ester.

[0027] The compound serving as component (A) is Q １ NH ２ group, and Q２ is a single bond or an alkylene group having 1 to 20 carbon atoms, and Q ３ is a single bond, —O—, —COO— or —OCO—, q1 is 0, q2 is 0, and Q ６ and Q ７ is a single bond, and Q ８ Also preferred is a compound (a-4) in which is an alkoxy group having 1 to 12 carbon atoms, a haloalkoxy group having 1 to 12 carbon atoms, a phenoxy group or a biphenyloxy group.

[0028] Specific examples of the compound (a-4) include 4-aminocinnamic acid methyl ester, 4-aminocinnamic acid ethyl ester, and the like.

[0029] The compound serving as component (A) is Q １ is a trialkoxysilyl group, and Q ２ is an alkylene group having 1 to 20 carbon atoms, and Q ３ is —O—, —COO—, or —OCO—, q1 is 0, q2 is 0, and Q ６ and Q ７ is a single bond, and Q ８ is also preferred a compound (a-5) in which is an alkoxy group having 1 to 12 carbon atoms, a haloalkoxy group having 1 to 12 carbon atoms, a phenoxy group, or a biphenyloxy group. The "alkoxy (group)" in the (tri)alkoxysilyl group can be an alkoxy (group) having 1 to 12 carbon atoms.

[0030] Specific examples of compound (a-5) include 4-(3-trimethoxysilylpropyloxy)cinnamic acid methyl ester, 4-(3-triethoxysilylpropyloxy)cinnamic acid methyl ester, 4-(3-trimethoxysilylpropyloxy)cinnamic acid ethyl ester, 4-(3-triethoxysilylpropyloxy)cinnamic acid ethyl ester, 4-(6-trimethoxysilylhexyloxy)cinnamic acid methyl ester, 4-(6-triethoxysilylhexyloxy)cinnamic acid methyl ester, 4-(6-trimethoxysilylhexyloxy)cinnamic acid ethyl ester, and 4-(6-triethoxysilylhexyloxy)cinnamic acid ethyl ester.

[0031] The compound serving as component (A) is Q １ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, or OH; ２ and Q ３ is a single bond, q1 is 0, q2 is 0, and Q ６ is a single bond or an oxygen atom, and Q ７ is an alkylene group having 1 to 20 carbon atoms, and Q ８ is an OH group, the compound (a-6) is preferred.

[0032] Examples of such compounds (a-6) include cinnamic acid 8-hydroxyoctyl ester, cinnamic acid 6-hydroxyhexyl ester, cinnamic acid 4-hydroxybutyl ester, cinnamic acid 3-hydroxypropyl ester, cinnamic acid 2-hydroxyethyl ester, and cinnamic acid hydroxymethyl ester.

[0033] The low molecular weight compound of component (A) is a compound represented by the formula (a) above, １ is a group represented by formula (c-1), and Q ２ is a single bond or an alkylene group having 1 to 20 carbon atoms, q1 is 0, q2 is 0, and Q ６ is a single bond, and Q ７ is a single bond, and Q ８ is an OH group, NH ２ Also preferred is compound (a-7), which is a group, a hydroxyphenoxy group, a carboxyphenoxy group, an aminophenoxy group, an aminocarbonylphenoxy group, a phenylamino group, a hydroxyphenylamino group, a carboxyphenylamino group, an aminophenylamino group, a hydroxyalkylamino group, a bis(hydroxyalkyl)amino group, a cyanophenylamino group, an alkoxy group having 1 to 12 carbon atoms, or a haloalkoxy group having 1 to 12 carbon atoms.

[0034] Specific examples of compound (a-7) which is component (A) include 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid, 4-(6-acryloxyhexyl-1-oxy)cinnamic acid, 4-(3-methacryloxypropyl-1-oxy)cinnamic acid, 4-(4-(3-methacryloxypropyl-1-oxy)phenoxy)benzoic acid, 4-(4-(6-methacryloxyhexyl-1-oxy)benzoyloxy)cinnamic acid, 4-(6-methacryloxyhexyl-1-oxy)cinnamamide, 4-(6-methacryloxyhexyl-1-oxy)-N-(4-cyanophenyl)cinnamamide, and 4-(6-methacryloxyhexyl-1-oxy)-N-bishydroxyethylcinnamamide.

[0035] The low molecular weight compound of component (A) is a compound represented by the formula (a) above: １ and A ２ At least one of Q represents a methyl group; １ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, or an OH group; Q ２ is a single bond or an alkylene group having 1 to 20 carbon atoms; ３ is a single bond or —O—, q1 is 0, q2 is 0, and Q ６ is a methylene group or a group represented by the following formula (c-2), (In the formula, * represents a bond.) Q ７ is an alkylene group having 1 to 20 carbon atoms, and Q ８ Also preferred is a compound (a-8) in which is an alkoxy group having 1 to 12 carbon atoms, a haloalkoxy group having 1 to 12 carbon atoms, a phenoxy group, a biphenyloxy group or a cyclohexyloxy group.

[0036] Specific examples of the compound (a-8) that is the component (A) include compounds represented by the following formula:

[0037] The low molecular weight compound of component (A) is a compound represented by the formula (a) above, １is a group represented by formula (c-1), and Q ２ is a single bond or an alkylene group having 1 to 20 carbon atoms, Q3 is —O—, q1 is 0, q2 is 0, and Q ６ is an oxygen atom, and Q ７ is an alkylene group having 1 to 20 carbon atoms, and Q ８ Also preferred is a compound (a-9) in which is an alkoxy group having 1 to 12 carbon atoms, a haloalkoxy group having 1 to 12 carbon atoms, a phenoxy group, or a biphenyloxy group.

[0038] Specific examples of the compound (a-9) that is the component (A) include compounds represented by the following formula:

[0039] The compounds exemplified above are １ and A ２ are both hydrogen atoms, but A of the above compound １ and A ２ Also preferred are α-methyl and β-methyl forms in which either one of the groups is a methyl group. Of the compounds exemplified above, the novel compounds can be produced from known raw materials according to the methods described in the examples.

[0040] The low-molecular-weight photoalignment component (A) may be, but is not limited to, the above specific examples. Component (A) may also be a mixture of one or more compounds.

[0041] [Component (B)] The cured film-forming composition of the present invention contains a polymer having an epoxy group as component (B). When component (B) is cured by a crosslinking reaction, the alignment material obtained from the composition of the present invention exhibits alignment properties and solvent resistance.

[0042] The polymer having an epoxy group can be, for example, a homopolymer of a polymerizable unsaturated compound having an epoxy group, or a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound.

[0043] Specific examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 6,7-epoxyheptyl α-ethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 4-hydroxybutyl methacrylate glycidyl ether, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, and 1,7-octadiene monoepoxide. Among these, 3,4-epoxycyclohexylmethyl acrylate and 3,4-epoxycyclohexylmethyl methacrylate are particularly preferred in terms of availability and the properties of the cured film obtained.

[0044] Examples of other polymerizable unsaturated compounds include (meth)acrylic acid alkyl esters, (meth)acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other polymerizable unsaturated compounds. Note that throughout this specification, (meth)acrylic means both acrylic and methacrylic.

[0045] Specific examples of these include alkyl methacrylate esters such as hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside, 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like; alkyl acrylate esters such as methyl acrylate and isopropyl acrylate; and cyclic alkyl methacrylate esters such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0]methyl methacrylate, cyclohexyl methacrylate, tricyclo[5.2.1.0]methyl ... ２，６ ] decan-8-yl methacrylate, tricyclo[5.2.1.0 ２，６ ] decan-8-yloxyethyl methacrylate, isobornyl methacrylate, cholestanyl methacrylate, etc.; acrylic acid cyclic alkyl esters such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ２，６ ] decan-8-yl acrylate, tricyclo[5.2.1.0 ２，６]decan-8-yloxyethyl acrylate, isobornyl acrylate, cholestanyl acrylate, etc.; methacrylic acid aryl esters such as phenyl methacrylate, benzyl methacrylate, etc.; acrylic acid aryl esters such as phenyl acrylate, benzyl acrylate, etc.; unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate, etc.; bicyclo unsaturated compounds such as bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, etc. , 5-ethylbicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxy 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, etc.; maleimide compounds such as phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, and N-succinimidyl-6-maleimidocaproate. ester, N-succinimidyl-3-maleimidopropionate, N-(9-acridinyl)maleimide, etc.; unsaturated aromatic compounds, for example, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, etc.; conjugated diene compounds, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.; unsaturated monocarboxylic acids, for example, acrylic acid, methacrylic acid, crotonic acid, etc.; unsaturated dicarboxylic acids, for example, maleic acid, fumaric acid, citraconic acid, mesaconic 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, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, etc.;

[0046] The copolymerization ratio of the polymerizable unsaturated compound having an epoxy group in the copolymer having an epoxy group is preferably 30% by mass or more, more preferably 50% by mass or more.

[0047] The synthesis of the (co)polymer having an epoxy group can be carried out by a known radical polymerization method, preferably in a solvent in the presence of a suitable polymerization initiator.

[0048] The weight average molecular weight (polystyrene equivalent) of the epoxy group-containing polymer, component (B), is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3,000 to 80,000.

[0049] These polymers may be used alone or in combination of two or more.

[0050] As the polymer having an epoxy group, a commercially available product may be used. Examples of such commercially available products include EHPE3150 and EHPE3150CE (manufactured by Daicel Corporation), UG-4010, UG-4035, UG-4040, and UG-4070 (manufactured by Toagosei Co., Ltd., ALUFON series), ECN-1299 (manufactured by Asahi Kasei Corporation), DEN431 and DEN438 (manufactured by The Dow Chemical Company), jER-152 (manufactured by Mitsubishi Chemical Corporation), Epicron N-660, N-665, N-670, N-673, N-695, N-740, N-770, and N-775 (manufactured by DIC Corporation), and EOCN-1020, EOCN-102S, and EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.).

[0051] The content of the polymer having an epoxy group as component (B) in the cured film-forming composition of the present invention is preferably 200 parts by mass to 1500 parts by mass, and more preferably 400 parts by mass to 1300 parts by mass, based on 100 parts by mass of the photoalignment component as component (A).

[0052] [Component (C)] The cured film-forming composition of the present invention further contains a thermal acid generator as component (C) in addition to the above-mentioned components (A) and (B). Component (C) is effective in accelerating the thermal curing reaction in the formation of a cured film using the cured film-forming composition that forms a cured film on the surface of the optical film of the present invention.

[0053] There are no particular limitations on the component (C), as long as it is a compound that undergoes thermal decomposition during pre-baking or post-baking to generate an acid, that is, a compound that undergoes thermal decomposition at a temperature of 60°C to 150°C to generate an acid.

[0054] Examples of the thermal acid generator include bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylene tris(methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-tosylate, N-ethyl-4-toluenesulfonamide, and compounds represented by the following formulae [TAG-1] to [TAG-41], as well as onium salts such as iodonium salts, sulfonium salts, phosphonium salts, and selenium salts.

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062] Examples of the iodonium in the iodonium salt include diaryliodoniums such as diphenyliodonium, 4,4'-dichlorodiphenyliodonium, 4,4'-dimethoxydiphenyliodonium, 4,4'-di-tert-butyldiphenyliodonium, 4-methylphenyl(4-(2-methylpropyl)phenyl)iodonium, 3,3'-dinitrophenyliodonium, 4-(1-ethoxycarbonylethoxy)phenyl(2,4,6-trimethylphenyl)iodonium, and 4-methoxyphenyl(phenyl)iodonium. Examples of the iodonium salt include diaryliodonium salts having the above-mentioned iodonium as the cation moiety and chloride, bromide, mesylate, tosylate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis(pentafluorophenyl)borate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, or the like as the anion moiety.

[0063] Examples of the sulfonium in the sulfonium salt include arylsulfonium such as triphenylsulfonium, diphenyl(4-tert-butylphenyl)sulfonium, tris(4-tert-butylphenyl)sulfonium, diphenyl(4-methoxyphenyl)sulfonium, tris(4-methylphenyl)sulfonium, tris(4-methoxyphenyl)sulfonium, tris(4-ethoxyphenyl)sulfonium, diphenyl(4-(phenylthio)phenyl)sulfonium, tris(4-(phenylthio)phenyl)sulfonium, benzyl(4-acetoxyphenyl)(methyl)sulfonium, 2-methylbenzyl(4-acetoxyphenyl)(methyl)sulfonium, and 4-methylbenzyl(4-hydroxyphenyl)(methyl)sulfonium. Examples of sulfonium salts include arylsulfonium salts in which the above-mentioned sulfonium is used as the cation moiety and chloride, bromide, trifluoromethanesulfonate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, tetrakis(pentafluorophenyl)borate, hexafluoroantimonate, or the like is used as the anion moiety.

[0064] Examples of the phosphonium in the phosphonium salt include arylphosphonium such as tetraphenylphosphonium, ethyltriphenylphosphonium, tetra(p-methoxyphenyl)phosphonium, ethyltri(p-methoxyphenyl)phosphonium, benzyltriphenylphosphonium, etc. Examples of the phosphonium salt include arylphosphonium salts having the above phosphonium as the cation moiety and chloride, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, or the like as the anion moiety.

[0065] The selenium salts include triarylselenium salts such as triphenylselenium hexafluorophosphate.

[0066] The component (C) is commercially available, and examples thereof include TA-100, TA-100FG, IK-1, and IK-1FG (all manufactured by San-Apro Ltd.), San-Aid (registered trademark) SI-B2A, San-Aid (registered trademark) SI-B7, San-Aid (registered trademark) SI-B3A, San-Aid (registered trademark) SI-B3, San-Aid (registered trademark) SI-B5, San-Aid (registered trademark) SI-B4, San-Aid (registered trademark) SI-150, San-Aid (registered trademark) SI-110, San-Aid (registered trademark) SI-60, San-Aid (registered trademark) SI-80, and San-Aid (registered trademark) SI-100 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

[0067] The content of component (C) in the cured film-forming composition of the present invention is 1 to 150 parts by mass, preferably 3 to 120 parts by mass, more preferably 5 to 100 parts by mass, and even more preferably 10 to 80 parts by mass, per 100 parts by mass of the photoalignment component (A). By ensuring that the content of component (C) is 1 part by mass or more, sufficient thermosetting properties and solvent resistance can be imparted, and high sensitivity to light exposure can also be imparted. Furthermore, by ensuring that the content is 150 parts by mass or less, the storage stability of the cured film-forming composition can be improved.

[0068] [Other Additives] The cured film-forming composition according to an embodiment of the present invention may contain other additives as long as the effects of the present invention are not impaired. Examples of other additives include a sensitizer. The sensitizer is effective in accelerating the photoreaction when forming a cured film on the surface of the optical film of the present invention.

[0069] Examples of the sensitizer include derivatives of benzophenone, anthracene, anthraquinone, thioxanthone, etc., and nitrophenyl compounds, etc. Among these, N,N-diethylaminobenzophenone, which is a benzophenone derivative, and 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4-nitrostilbene, 4-nitrobenzophenone, and 5-nitroindole, which are nitrophenyl compounds, are particularly preferred.

[0070] These sensitizers are not particularly limited to those mentioned above, and these can be used alone or in combination of two or more compounds.

[0071] In an embodiment of the present invention, when a sensitizer is used, the proportion used is preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass, per 100 parts by mass of component (A). If this proportion is too small, the effect of the sensitizer may not be fully obtained, whereas if it is too large, the transmittance of the formed cured film may decrease or the coating film may become rough.

[0072] Furthermore, the cured film-forming composition according to an embodiment of the present invention may contain other additives such as a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, and an antioxidant, as long as the effects of the present invention are not impaired.

[0073] [Solvent] The cured film-forming composition according to the embodiment of the present invention can be used in the form of a solution (varnish) dissolved in a solvent. The solvent used in this case dissolves the components (A), (B), and (C) and, if desired, other additives, and the type and structure of the solvent are not particularly limited as long as it has the ability to dissolve them.

[0074] Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, cyclopentyl methyl ether, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, and 3-methyl-2-pentanone. , 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, n-propyl acetate, isopropyl acetate, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. These solvents can be used alone or in combination of two or more.

[0075] The solvent is also commercially available. Examples of commercially available mixed solvents include Neoethanol (registered trademark) PM, Neoethanol (registered trademark) MIP, Neoethanol (registered trademark) IPM, Neoethanol (registered trademark) IPE, Neoethanol (registered trademark) PHI, Neoethanol (registered trademark) MHI, Neoethanol (registered trademark) PIP, Neoethanol (registered trademark) HIMTE, Neoethanol (registered trademark) PHM, Neoethanol (registered trademark) IPME, and Neoethanol (registered trademark) P-7 (all manufactured by Taishin Chemical Co., Ltd.).

[0076] Of these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, cyclohexanone, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and Neoethanol (registered trademark) IPM are more preferred due to their good film-forming properties and high safety.

[0077] <Preparation of cured film-forming composition> As described above, the cured film-forming composition of the present invention comprises the compound represented by the above formula (a) (photoalignment component) as component (A), the polymer having an epoxy group as component (B), and the thermal acid generator as component (C), and in one embodiment, further comprises a solvent, and the above-mentioned components can be dissolved in the solvent. The cured film-forming composition of the present invention can also contain other additives as long as the effects of the present invention are not impaired.

[0078] Preferred examples of the cured film-forming composition of the present invention are as follows: [1]: A cured film-forming composition containing the component (A), 400 parts by mass to 1,300 parts by mass of the component (B) based on 100 parts by mass of the component (A), and 1 part by mass to 150 parts by mass of the component (C) based on 100 parts by mass of the component (A).

[0079] The blending ratios, preparation methods, etc., when the cured film-forming composition of the present invention is used as a solution (in the form of a so-called varnish) are described in detail below. The solid content of the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 80% by mass, preferably 2% by mass to 60% by mass, and more preferably 3% by mass to 40% by mass. Here, the solid content refers to all components of the cured film-forming composition excluding the solvent.

[0080] The method for preparing the cured film-forming composition of the present invention is not particularly limited. Examples of the preparation method include a method in which components (A) and (C) are mixed in a predetermined ratio with a solution of component (B) dissolved in a solvent to obtain a homogeneous solution, or a method in which other additives are further added as necessary at an appropriate stage of this preparation method and mixed. In this case, component (C) may be added later, for example, immediately before use of the composition, in order to improve the storage stability of the composition.

[0081] In preparing the cured film-forming composition of the present invention, as described above, the solution of component (B) obtained by polymerization in a solvent can be used as is. In this case, for example, the component (A) and the component (C) can be added to a solution of component (B) obtained by (co)polymerizing the above-mentioned polymerizable unsaturated compound having an epoxy group and, if desired, other polymerizable unsaturated compounds to obtain a uniform solution of the cured film-forming composition. In this case, additional solvent may be added for the purpose of adjusting the concentration. In this case, the solvent used in the production process of component (B) and the solvent used to adjust the concentration of the cured film-forming composition may be the same or different.

[0082] The prepared solution of the composition for forming a cured film is preferably filtered using a filter having a pore size of about 0.2 μm before use in forming a cured film.

[0083] <Cured Film, Alignment Material, and Retardation Material> The cured film of the present invention can be formed by applying the above-mentioned cured film-forming composition (a solution thereof) onto a substrate (e.g., a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, an ITO substrate, etc.) or a film (e.g., a resin film such as a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, or an acrylic film) by bar coating, spin coating, flow coating, roll coating, slit coating, spin coating followed by slit coating, inkjet coating, printing, or the like to form a coating film, and then heating and drying the coating on a hot plate, in an oven, or the like.

[0084] The heating and drying conditions are such that, when a cured film is used as a liquid crystal alignment film as described below, the curing reaction proceeds to such an extent that the components of the liquid crystal alignment film are not eluted into the polymerizable liquid crystal solution to be applied thereon, and for example, a heating temperature and heating time appropriately selected from the ranges of 50°C to 150°C and 0.4 to 60 minutes are employed. The heating temperature and heating time are preferably 60°C to 130°C and 0.5 to 10 minutes.

[0085] The thickness of the cured film of the present invention is, for example, 0.05 μm to 5 μm, and can be appropriately selected taking into consideration the step and optical and electrical properties of the film used as the substrate or base material.

[0086] The cured film of the present invention thus prepared can be irradiated with polarized UV light to function as a liquid crystal alignment film, i.e., as a component for aligning compounds having liquid crystallinity, including polymerizable liquid crystals, on a substrate, and thus the cured film can be used as an alignment material. This alignment material is also within the scope of the present invention.

[0087] The polarized UV irradiation method generally uses ultraviolet to visible light with a wavelength of 150 nm to 450 nm, and is carried out by irradiating linearly polarized light from a vertical or oblique direction at room temperature or in a heated state.

[0088] Since the alignment material formed from the cured film-forming composition of this embodiment has solvent resistance and heat resistance, a retardation material composed of a polymerizable liquid crystal solution can be applied to this alignment material, and then heated to the liquid crystal phase transition temperature to convert the retardation material into a liquid crystal state and align it on the alignment material. The retardation material in the desired alignment state can then be cured as is to form a retardation material having a layer with optical anisotropy. The alignment material formed from the cured film-forming composition of the present invention can also be used to transfer the cured retardation material. Specifically, as described above, the retardation material in the oriented state on the alignment material is cured as is to form a cured layer, and a laminate of the alignment material and the cured layer (of the retardation material) is formed. The surface of the cured layer derived from the retardation material of the laminate is then attached to a transfer recipient via an adhesive layer or a adhesive layer. The cured layer derived from the retardation material in the laminate is then peeled off from the alignment material, and the cured layer derived from the retardation material is transferred onto the transfer recipient as a layer with optical anisotropy, thereby obtaining a retardation material. The retardation material thus obtained is also within the scope of the present invention, that is, the cured film-forming composition of the present invention can also function as a resin composition for forming a retardation material.

[0089] The transfer object can be, for example, an optical member such as a polarizing plate or a retardation plate, or a transfer substrate. The retardation plate can be, for example, a plate having a retardation layer that is a liquid crystal layer, or a stretched film. The adhesive layer and the bonding layer can be made of a pressure-sensitive adhesive or adhesive that has adhesion to both the retardation layer (a cured layer derived from a retardation material) and the transfer object. The pressure-sensitive adhesive and adhesive can be any of those commonly used in the method for producing a retardation plate by a transfer method.

[0090] As the retardation material, for example, a liquid crystal monomer having a polymerizable group and a composition containing the same can be used.In the present invention, when the substrate on which the alignment material is formed or the transfer object on which the cured layer derived from the retardation material is transferred is a film, the retardation material of the present invention can be used as a retardation film.The retardation material forming such a retardation material can be in a liquid crystal state and can take an alignment state such as horizontal alignment, cholesteric alignment, vertical alignment, hybrid alignment, etc. on the alignment material, and can be used according to the retardation properties required.

[0091] Furthermore, when manufacturing a patterned retardation material for use in a 3D display, the cured film on the surface of the alignment material of the present invention is exposed to polarized UV light through a line-and-space pattern mask at an angle of, for example, +45 degrees from a predetermined reference, and then the mask is removed and exposed to polarized UV light at a lower exposure dose at an angle of -45 degrees. This converts the cured film on the film surface into a liquid crystal alignment film in which two types of liquid crystal alignment domains with different liquid crystal alignment control directions are formed, and the optical film can be used as an alignment material. A retardation material made of a polymerizable liquid crystal solution is then applied to the alignment material, and the retardation material is then placed in a liquid crystal state by heating to the liquid crystal phase transition temperature. The polymerizable liquid crystal in the liquid crystal state is oriented on the alignment material in which the two types of liquid crystal alignment domains are formed, forming alignment states corresponding to each liquid crystal alignment domain. The retardation material in this alignment state is then cured as is, and the above-mentioned alignment state is fixed, resulting in a patterned retardation material in which two types of retardation domains with different retardation characteristics are regularly arranged. Furthermore, a patterned retardation material can also be obtained by transferring the retardation material with the orientation state fixed onto a transfer target as described above.

[0092] The cured film of the present invention can also be used as a liquid crystal alignment film for a liquid crystal display element. For example, a liquid crystal display element in which the liquid crystal is aligned can be produced by using substrates on which the cured film of the present embodiment formed as described above is formed, and then laminating the substrates with the alignment materials facing each other via a spacer, and then injecting liquid crystal between the substrates. Therefore, the cured film of the present invention can be suitably used for producing various retardation materials (retardation films), liquid crystal display elements, etc.

[0093] EXAMPLES The present invention will be specifically described below with reference to examples of the present invention, but the present invention should not be construed as being limited to these examples.

[0094] [Abbreviations used in Examples] The meanings of the abbreviations used in the following examples are as follows: <Raw Materials> M100: Cyclomer M-100 (manufactured by Daicel Corporation, 3,4-epoxycyclohexylmethyl methacrylate) MMA: methyl methacrylate MAIB: 2,2'-azobis(isobutyrate) dimethyl

[0095] <Component A> CIN1: 4-methoxycinnamic acid

[0096] CIN2:

[0097] CIN3:

[0098] CIN4:

[0099] CIN5:

[0100] CIN6:

[0101] CIN8:

[0102] CIN9:

[0103] CIN10:

[0104] CIN11:

[0105] CIN12:

[0106] CIN13:

[0107] <Catalyst> B2A: San-Aid (registered trademark) SI-B2A (manufactured by Sanshin Chemical Industry Co., Ltd.) (thermal acid generator)

[0108] B7: San-Aid (registered trademark) SI-B7 (manufactured by Sanshin Chemical Industry Co., Ltd.) (thermal acid generator) TA: Trimellitic anhydride (acid catalyst) 2E4MEZ: 2-ethyl-4-methylimidazole (base catalyst)

[0109] <Other additives> PHS: VP-15000 (Nippon Soda Co., Ltd., polyparahydroxystyrene) BZA: benzoic acid 4MBZA: 4-methoxybenzoic acid

[0110] CIN7: cinnamic acid

[0111] <Solvents> PMA: Propylene glycol monomethyl ether acetate BA: Butyl acetate CPN: Cyclopentanone MEK: Methyl ethyl ketone THF: Tetrahydrofuran AcOEt: Ethyl acetate

[0112] <Measurement of Weight Average Molecular Weight> Apparatus: GPC apparatus (HLC-8320) manufactured by Tosoh Corporation Column: TSKgel (registered trademark) α-4000 and TSKgel (registered trademark) α-3000 manufactured by Tosoh Corporation Column oven: 40°C Flow rate: 1 mL / min Eluent: N,N-dimethylformamide Standard sample: polystyrene

[0113] < １ H-NMR Measurement> Apparatus: Fourier transform superconducting nuclear magnetic resonance spectrometer (FT-NMR) "AVANCE III" (manufactured by BRUKER) 500 MHz. Solvent: deuterated dimethyl sulfoxide (DMSO-d ６ ) or deuterated chloroform (CDCl ３ ). Standard substance: tetramethylsilane (TMS).

[0114] <Synthesis of Component A> <Synthesis Example 1 (Synthesis of CIN10)>

[0115] CIN8 (12.2 g, 50 mmol) and THF (146 g) were placed in a 500 mL four-neck flask, and after replacing the atmosphere with nitrogen, the flask was cooled to 0°C and chloromethyl ethyl ether (5.4 g, 58 mmol) was added dropwise. ３ N, 6.1 g, 60 mmol) was slowly added dropwise, and after confirming that the heat generation had subsided, the mixture was stirred at room temperature. After the reaction was completed, AcOEt (160 g) and ion-exchanged water (160 g) were added to the reaction solution, and the organic phase was extracted. The obtained organic phase was washed twice with ion-exchanged water (160 g) and concentrated to obtain 14.9 g of CIN10 (colorless, transparent liquid, yield 98%).

[0116] １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 7.64 (s, 1H), 7.41-7.43 (d, 2H), 7.28-7.29 (d, 2H), 5.37 (s, 2H), 3.67-3.71 (m, 2H), 2.49-2.52 (m, 1H) ), 2.07 (s, 3H), 1.77-1.79 (d, 4H), 1.68-1.71 (d, 1H), 1.32-1.44 (m, 4H), 1.21-1.27 (m, 1H), 1.14-1.17 (t, 3H).

[0117] <Synthesis Example 2 (Synthesis of CIN11)>

[0118] CIN9 (12.2 g, 50 mmol) and THF (146 g) were placed in a 500 mL four-neck flask, and after replacing the atmosphere with nitrogen, the flask was cooled to 0°C and chloromethyl ethyl ether (5.4 g, 58 mmol) was added dropwise. ３ N, 6.1 g, 60 mmol) was slowly added dropwise, and after confirming that the heat generation had subsided, the mixture was stirred at room temperature. After the reaction was completed, AcOEt (160 g) and ion-exchanged water (160 g) were added to the reaction solution, and the organic phase was extracted. The obtained organic phase was washed twice with ion-exchanged water (160 g) and concentrated to obtain 15.1 g of CIN11 (light yellow liquid, 100% yield).

[0119] １ H-NMR (500MHz) in DMSO-d ６ ​​: δ (ppm) = 7.50-7.52 (d, 2H), 7.25-7.26 (d, 2H), 6.16 (s, 1H), 5.31 (s, 2H), 3.63-3.67 (m, 2H), 2.50-2.52 (m, 4H), 1.76-1.79 (d, 4H), 1.68-1.71 (d, 1H), 1.34-1.41 (m, 4H), 1.21-1.26 (m, 1H), 1.13-1.16 (t, 3H).

[0120] <Synthesis Example 3 (Synthesis of CIN12)>

[0121] A 500 mL four-neck flask was charged with (E)-3-(4-hexylphenyl)-2-butenoic acid (11.3 g, 45.9 mmol) and THF (136 g), and after replacing the atmosphere with nitrogen, the flask was cooled to 0°C and chloromethyl ethyl ether (5.7 g, 60.7 mmol) was added dropwise. ３ N, 6.4 g, 63.3 mmol) was slowly added dropwise, and after confirming that the heat generation had subsided, the mixture was stirred at room temperature. After completion of the reaction, AcOEt (150 g) and ion-exchanged water (150 g) were added to the reaction solution, and the organic phase was extracted. The obtained organic phase was washed twice with ion-exchanged water (150 g) and concentrated to obtain 13.1 g of CIN12 (colorless, transparent liquid, yield 94%).

[0122] １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 7.52-7.51 (d, 2H), 7.25-7.23 (d, 2H), 6.17 (d, 1H), 5.31 (s, 2H), 3.68-3.63 (q, 2H), 2.61-2 .58 (t, 2H), 2.52 (d, 3H), 1.59-1.54 (m, 2H), 1.30-1.25 (m, 6H), 1.16-1.13 (t, 3H), 0.87-0.84 (t, 3H).

[0123] <Synthesis Example 4 (Synthesis of CIN13)>

[0124] ​A 500 mL four-neck flask was charged with (E)-3-(4-hexyloxyphenyl)-2-butenoic acid (8.0 g, 30.5 mmol) and THF (96 g), and after replacing the atmosphere with nitrogen, the flask was cooled to 0°C and chloromethyl ethyl ether (3.3 g, 35.1 mmol) was added dropwise. ３ N, 3.7 g, 36.6 mmol) was slowly added dropwise, and after confirming that the heat generation had subsided, the mixture was stirred at room temperature. After completion of the reaction, AcOEt (100 g) and ion-exchanged water (100 g) were added to the reaction solution, and the organic phase was extracted. The obtained organic phase was washed twice with ion-exchanged water (100 g) and concentrated to obtain 9.0 g of CIN13 (light yellow liquid, yield 92%).

[0125] １ H-NMR (500MHz) in CDCl ３ : δ (ppm) = 7.46-7.44 (d, 2H), 6.90-6.88 (d, 2H), 6.13 (d, 1H), 5.37 (s, 2H), 3.99-3.97 (t, 2H), 3.75-3.71 (q, 2H) ), 2.58 (d, 3H), 1.82-1.76 (m, 2H), 1.49-1.43 (m, 2H), 1.36-1.32 (m, 4H), 1.27-1.24 (t, 3H), 0.92-0.90 (t, 3H).

[0126] Synthesis of Component B Synthesis Example 5 M100 (37.6 g, 191.6 mmol) and MAIB (0.441 g, 1.92 mmol) as a polymerization catalyst were dissolved in a PMA / BA=5 / 5 (mass ratio) mixed solvent (57.1 g), and this solution was then added dropwise over 60 minutes to a flask containing a PMA / BA=5 / 5 (mass ratio) mixed solvent (95.1 g) maintained at 80°C. After completion of the dropwise addition, the mixture was allowed to react overnight to obtain a solution of an acrylic polymer having epoxy groups (PB-1) (solids concentration 20% by mass). The weight average molecular weight Mw of the resulting acrylic polymer having epoxy groups was 52,460.

[0127] ​<Synthesis of Other Additives> <Synthesis Example 6> MMA (35.6 g, 355.6 mmol) and MAIB (2.46 g, 10.7 mmol) as a polymerization catalyst were dissolved in PMA (57.1 g), and this solution was then added dropwise over 60 minutes to a flask containing PMA (95.1 g) maintained at 80°C. After completion of the addition, the mixture was allowed to react overnight to obtain an acrylic polymer solution (PMMA) (solids concentration 20% by mass). The weight-average molecular weight Mw of the obtained acrylic polymer was 12,570.

[0128] Preparation Example 1: CIN1 (10 parts by mass) was used as the component (A) and PB-1 (90 parts by mass) obtained in Synthesis Example 1 was used as the component (B) and PMA and BA were added to the mixture so that the solvent composition was PMA:BA = 40:60 (mass ratio), and the mixture was stirred for 2 hours. Dissolution was confirmed visually, 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 solids concentration of 8.0 mass%.

[0129] Preparation Examples 2 to 20 (A-2) to (A-15) and (B-1) to (B-5) were prepared in the same manner as in Preparation Example 1, except that the types and amounts of each component were changed as shown in Table 1 below. In Table 1, for "Component A," "Component B," and "Other Additives," [parts by mass] indicates the value of the solid content (value excluding the solvent).

[0130]

[0131] Preparation of Catalyst Solution Preparation Example 21 1.0 g of B2A as a catalyst and 19.0 g of BA as a solvent were added, stirred for 1 hour, and visually confirmed to be dissolved. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a catalyst solution (C-1).

[0132] Preparation Example 22: 1.0 g of B7 as a catalyst and 19.0 g of BA as a solvent were added, stirred for 1 hour, and visually confirmed to be dissolved. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a catalyst solution (C-2).

[0133] Preparation Example 23: TA (1.0 g) as a catalyst and PMA (19.0 g) as a solvent were added, stirred for 1 hour, and visually confirmed to be dissolved. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a catalyst solution (C-3).

[0134] Preparation Example 24: 2E4MEZ (1.0 g) as a catalyst and BA (19.0 g) as a solvent were added, stirred for 1 hour, and visually confirmed to be dissolved. The solution was filtered through a filter with a pore size of 0.2 μm to prepare a catalyst solution (C-4).

[0135] <Preparation of cured film-forming composition and liquid crystal aligning agent> <Example 1-1> C-1 (0.16 g) obtained in Preparation Example 21 and BA (0.54 g) as a dilution solvent were added to A-1 (2.00 g) obtained in Preparation Example 1, and the mixture was stirred for 1 minute to obtain a cured film-forming composition (AL-1). (AL-1) was used as it was as a liquid crystal aligning agent.

[0136] Examples 1-2 to 1-22, Comparative Examples 1-1 to 1-11 Cured film-forming compositions (AL-2) to (AL-22) and (BL-1) to (BL-11) were prepared in the same manner as in Example 1-1, except that the types and amounts of each component shown in Table 2 below were used. (AL-2) to (AL-22) and (BL-1) to (BL-11) were used as liquid crystal aligning agents as they were. In Table 2, the "composition" and "catalyst" terms refer to the mass of the composition including the solvent or the catalyst solution itself.

[0137]

[0138] <Preparation of polymerizable liquid crystal solution for horizontal alignment> Paliocolor (registered trademark) LC-242 (manufactured by BASF Japan Ltd.) (19.3 g), which is a polymerizable liquid crystal for horizontal alignment, Omnirad (registered trademark) 907 (manufactured by IGM Resins B.V.) (0.6 g) as a photoradical initiator, and BYK (registered trademark)-361N (manufactured by BYK Japan KK) (0.1 g) as a leveling agent were added, and CPN (80 g) was further added as a solvent, followed by stirring for 2 hours and visually confirming that the mixture had dissolved, thereby obtaining a 20 mass % polymerizable liquid crystal solution (LC-1).

[0139] <Formation of Liquid Crystal Alignment Film and Preparation of Retardation Film> <Example 2-1> The liquid crystal alignment agent (AL-1) obtained in Example 1-1 was applied to a TAC film substrate using a bar coater to a wet film thickness of 4 μm. The film was dried by heating at 120° C. for 2 minutes in a hot air circulation oven to form a cured film on the film. Next, linearly polarized light with a wavelength of 313 nm was applied to the surface of this cured film at 20 mJ / cm ２ The above-mentioned polymerizable liquid crystal solution LC-1 for horizontal alignment was applied to the above-mentioned liquid crystal alignment film with a wet film thickness of 8 μm using a bar coater. Then, the film was dried by heating in an oven at 100°C for 2 minutes, and then irradiated with unpolarized light of 365 nm wavelength at 500 mJ / cm under a nitrogen atmosphere. ２ The polymerizable liquid crystal was cured by vertical irradiation with an exposure amount of 10 ...

[0140] Examples 2-2 to 2-32, Comparative Examples 2-1 to 2-11 Retardation films were produced in the same manner as in Example 2-1, except that the type of liquid crystal aligning agent used and the heating and drying conditions during cured film formation were changed as shown in Table 3.

[0141] The retardation films prepared above were evaluated by the following methods. The evaluation results are shown in Table 3.

[0142] [Evaluation of Orientation] The prepared retardation film on the substrate was sandwiched between a pair of polarizing plates, and the state of expression of retardation properties under crossed Nicols was visually observed. When the retardation film exhibits retardation, light is transmitted evenly when rotated 45°, with the angle at which light does not transmit being 0°. When there are defects due to disordered alignment of the liquid crystal, light transmission defects occur. The results were recorded in the "Orientation" column as "excellent" when retardation is exhibited without defects, "good" when retardation is exhibited but with defects, and "poor" when no retardation is exhibited.

[0143]

[0144] [Evaluation of Transferability] Using the liquid crystal aligning agents (AL-19) to (AL-22), the retardation film on the substrate (TAC film) prepared according to the procedure described above in <Formation of Liquid Crystal Alignment Film and Preparation of Retardation Film> was attached to a glass substrate via a transparent optical adhesive film (LUCIACS, manufactured by Nitto Denko Corporation). The laminate of the TAC film and liquid crystal alignment film serving as the substrate was then peeled off from the cured polymerizable liquid crystal, thereby transferring a retardation layer made of polymerizable liquid crystal to the glass substrate. The transferred retardation layer was evaluated using the following method. The evaluation results are shown in Table 4. [Evaluation of Alignment of Transferred Retardation Layer] The glass substrate to which the retardation layer had been transferred was sandwiched between a pair of polarizing plates, and the expression of retardation characteristics under crossed Nicols was visually observed. When rotated 45°, assuming an angle at which light does not transmit, light was transmitted evenly. If there were areas where the film was not transferred or if there were defects due to disturbances in the alignment of the liquid crystal, light transmission defects would occur. The results were recorded in the "Transferability" column as "Excellent" when the phase difference was expressed without any defects, "Good" when the phase difference was expressed but with defects, and "Poor" when no phase difference was expressed.

[0145]

[0146] [Evaluation of Solvent Resistance] The liquid crystal aligning agents (AL-1) to (AL-22), (BL-1) to (BL-11) obtained in Examples 1-1 to 1-22 and Comparative Examples 1-1 to 1-11 were spin-coated onto a silicon wafer substrate using a spin coater at 1000 rpm for 30 seconds, followed by heat drying on a hot plate at the temperature and time shown in Table 5 below to form a cured film. This cured film was immersed in CPN for 60 seconds, then spun at 3000 rpm for 30 seconds using a spin coater, and then heat dried on a hot plate at a temperature of 100°C for 30 seconds. The film thickness was measured before and after immersion in CPN, and the residual film ratio was calculated. The film thickness was measured using a FILMETRICS F20. The higher the residual film ratio, the better the solvent resistance. The results are shown in Table 5.

[0147]

[0148] As is clear from the results in Tables 3 and 5, all of the retardation films obtained from the cured film-forming compositions containing the components (A), (B), and (C) according to the present invention had good liquid crystal alignment properties and also good solvent resistance. Furthermore, as shown in the results in Table 4, it was confirmed that the cured film (liquid crystal alignment film) of the cured film-forming composition according to the present invention can transfer a cured product (retardation layer) of a polymerizable liquid crystal. In contrast, the cured film-forming composition according to the present invention that does not contain the components (A), (B), or (C) did not provide sufficient liquid crystal alignment properties.

[0149] The film having the cured film formed thereon according to the present invention is very useful as a liquid crystal alignment material for liquid crystal display elements or as an alignment material for forming optically anisotropic films provided inside or outside liquid crystal display elements, and is particularly suitable as a material for forming patterned retardation materials for 3D displays.Furthermore, it is also suitable as a material for forming cured films such as protective films, planarizing films, and insulating films in various displays such as thin film transistor (TFT) liquid crystal display elements and organic EL elements, and is particularly suitable as a material for forming interlayer insulating films in TFT liquid crystal elements, protective films in color filters, or insulating films in organic EL elements.

Claims

1. A composition for forming a cured film, comprising: (A) a compound represented by the following formula (a); (B) a polymer having an epoxy group; and (C) a thermal acid generator. [In the formula, A １ and A ２ each independently represents a hydrogen atom, a methyl group, or a cyano group. １ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, a di(alkyl)amino group having 1 to 6 carbon atoms, an OH group, or an NH ２ a group, a carboxy group, a trialkoxysilyl group, a cyano group, a nitro group, or a group represented by the following formula (c-1): (In formula (c-1), the dashed line represents Q ２ represents a bond with １０１ is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of this alkylene group may be replaced by a fluorine atom or an organic group. １０１ -CH in ２ CH ２ - may be replaced by -CH=CH-, and further, when any of the following groups are not adjacent to each other, the alkylene group may be interrupted by a group selected from the group consisting of -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO-, and M １ represents a hydrogen atom or a methyl group; ２ represents a single bond or an alkylene group having 1 to 20 carbon atoms, which may be branched or linear; Q ３ represents a single bond, —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, or —CO—, with the proviso that Q ２ If is a single bond, Q ３ is also a single bond, and Q ４ represents a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent fused ring group; Q ５ represents a single bond, an oxygen atom, —CO—, —COO—, or —OCO—; q1 is an integer of 0 to 3; q2 is 0 or 1; and Q ６ represents a single bond, an oxygen atom or a sulfur atom; ７ represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear, and Q ６ When Q is a single bond, ７ is a single bond, and Q ８ is an OH group, NH ２ Q represents a hydroxyphenoxy group, a carboxyphenoxy group, an aminophenoxy group, an aminocarbonylphenoxy group, a phenylamino group, a hydroxyphenylamino group, a carboxyphenylamino group, an aminophenylamino group, a hydroxyalkylamino group, a bis(hydroxyalkyl)amino group, an alkoxysilyl group, a cyanophenylamino group, an alkoxy group having 1 to 12 carbon atoms, a haloalkoxy group having 1 to 12 carbon atoms, a cycloalkoxy group having 3 to 12 carbon atoms, a phenoxy group, or a biphenyloxy group, ２ , Q ３ , Q ６ and Q ７ are both single bonds, q1 is 0, and Q ８ When Q is an OH group, １ represents a group other than a hydrogen atom as defined above.

2. The cured film-forming composition according to claim 1, wherein q2 is 0.

3. A cured film-forming composition according to claim 1, wherein the polymer having an epoxy group of component (B) is a homopolymer of a polymerizable unsaturated compound having an epoxy group or a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound.

4. The composition for forming a cured film according to claim 1, wherein the thermal acid generator (C) is a sulfonium salt.

5. An alignment material obtained by using the composition for forming a cured film according to any one of claims 1 to 4.

6. A retardation material formed using a cured film obtained from the composition for forming a cured film according to any one of claims 1 to 4.

7. A compound represented by the following formula (a): [In the formula, A １ and A ２ each independently represents a hydrogen atom, a methyl group, or a cyano group; A １ and A ２ At least one of Q represents a methyl group. １ represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms, or an OH group; Q ２ represents a single bond or an alkylene group having 1 to 20 carbon atoms, which may be branched or linear; Q ３ represents a single bond or —O—, provided that Q ２ If is a single bond, Q ３ is also a single bond, q1 is 0, q2 is 0, and Q ６ represents an oxygen atom, and Q ７ represents a methylene group or a group represented by the following formula (c-2): (In the formula, * represents a bond.) Q ８ represents an alkoxy group having 1 to 12 carbon atoms, a haloalkoxy group having 1 to 12 carbon atoms, a phenoxy group, a biphenyloxy group, or a cyclohexyloxy group.] 8. A compound represented by the formula:

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