Curable resin composition, cured film, and display device

Abstract

To provide a curable resin composition capable of forming a cured product excellent in light diffusibility and hardness.SOLUTION: A curable resin composition is provided. The curable resin composition contains a resin (A), a polymerizable compound (B), a polymerization initiator (C), and polymer particles (D). The resin (A) is a polymer including a structural unit having an aromatic heterocyclic ring.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition, a cured film, and a display device. [Background technology]

[0002] In image display devices such as organic electroluminescence (EL), curable resin compositions are used to form overcoats (top overcoats or bottom overcoats), etc. Known examples of such curable resin compositions include a curable resin composition containing a resin, a polymerizable compound, a polymerization initiator, and scattering particles (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2023-075911 Summary of the Invention [Problem to be solved by the invention]

[0004] However, in image display devices such as organic EL devices, the problem of unevenness due to reflection of external light can occur, and therefore, a curable resin composition for forming an overcoat or the like is required to have sufficient light diffusibility and to be able to form a cured film having sufficient hardness.

[0005] A main object of the present invention is to provide a curable resin composition that can form a cured product that has excellent light diffusibility and hardness. [Means for solving the problem]

[0006] The present invention provides the curable resin compositions described in [1] to [5], the cured film described in [6], and the solid-state imaging device described in [7]. [1] A composition comprising a resin (A), a polymerizable compound (B), a polymerization initiator (C), and polymer particles (D), The curable resin composition, wherein the resin (A) is a polymer containing a structural unit having an aromatic heterocycle. [2] The curable resin composition according to [1], wherein the polymerizable compound (B) includes a polymerizable compound having a condensed ring. [3] The curable resin composition according to [2], which satisfies the following formula (1): 0<[(x+y)×z]≦26.0 (1) [In formula (1), x represents the ratio (unit: mol / g) of the content (unit: parts by mass) of the polymer containing a structural unit having an aromatic heterocycle per 1 mol of the aromatic heterocycle, when the total mass of the resin (A) and the polymerizable compound (B) is taken as 100, or the sum thereof; y represents the ratio (unit: mol / g) of the content (unit: parts by mass) of the polymerizable compound having a fused ring per 1 mole of the fused ring, when the total mass of the resin (A) and the polymerizable compound (B) is taken as 100, or the sum thereof; z represents the content (unit: parts by mass) of the polymer particles (D) when the total mass of the resin (A) and the polymerizable compound (B) is taken as 100.] [4] The curable resin composition according to any one of [1] to [3], wherein the aromatic heterocycle is a carbazole ring. [5] The curable resin composition according to any one of [1] to [4], wherein the polymer particles (D) have an average particle size of 100 to 2300 nm. [6] A cured film obtained by curing the curable resin composition according to any one of [1] to [5]. [7] A display device comprising the cured film according to [6]. [Effects of the Invention]

[0007] According to the present invention, there is provided a curable resin composition capable of forming a cured product having excellent light diffusibility and hardness. Also, according to the present invention, there is provided a cured film obtained by curing such a curable resin composition. Furthermore, according to the present invention, there is provided a display device including such a cured film. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0009] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in this specification, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in numerical ranges described in this specification, the upper or lower limit value of that numerical range may be replaced with a value shown in an example.

[0010] In this specification, (meth)acrylate means acrylate or the corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl group, (meth)acrylic acid ester, (meth)acrylic resin, etc.

[0011] In this specification, unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more within the range that meets the conditions. When multiple substances corresponding to each component are present, the content of each component means the total amount of the multiple substances unless otherwise specified.

[0012] [Curable resin composition] The curable resin composition of the present embodiment contains a resin (A), a polymerizable compound (B), a polymerization initiator (C), and polymer particles (D). The curable resin composition of the present embodiment may further contain a solvent (E), a polymerization initiator aid (F), other components, and the like.

[0013] <Resin (A)> Resin (A) is mainly used as a binder resin for the curable resin composition. Resin (A) is preferably an alkali-soluble resin. The alkali-soluble resin refers to a resin that contains an acid group and is soluble in an alkaline developer. Examples of the acid group include a carboxy group, a sulfo group, and a phenolic hydroxy group.

[0014] Resin (A) is a polymer containing a structural unit having an aromatic heterocycle (hereinafter, sometimes referred to as "structural unit (Aa)"). The aromatic heterocycle is preferably a nitrogen-containing aromatic heterocycle, more preferably a carbazole ring. Resin (A) is not particularly limited as long as it contains the structural unit (Aa). For example, it may be a copolymer containing the structural unit (Aa), a structural unit having an α,β-unsaturated carbonyl group (hereinafter, sometimes referred to as "structural unit (Ab)"), and a structural unit (Ac) having an acid group (hereinafter, sometimes referred to as "structural unit (Ac)"). The copolymer may further contain other structural units (hereinafter, sometimes referred to as "structural unit (Ad)").

[0015] (Structural unit (Aa)) The structural unit (Aa) is a structural unit derived from an unsaturated compound having an aromatic heterocycle. The aromatic heterocycle may have a substituent. The structural unit can be obtained by copolymerizing a compound having an aromatic heterocycle as a monomer. Alternatively, the structural unit can be obtained by reacting another structural unit (Aa') with a compound (Aa'') having an aromatic heterocycle. When the resin (A) contains the structural unit (Aa), the light diffusion properties and hardness of the resulting cured film can be improved.

[0016] The aromatic heterocycle may be a monocycle or a fused ring. Here, the fused ring refers to a ring formed by two or more rings sharing one edge of each ring. The aromatic heterocycle is an n-valent aromatic heterocycle, and the n-valency may be, for example, monovalent or divalent. The n-valent aromatic heterocycle refers to the atomic group remaining after removing n hydrogen atoms from the hydrogen atoms directly bonded to the carbon atoms or heteroatoms constituting the ring of an aromatic heterocyclic compound. A monovalent aromatic heterocycle is an atomic group remaining after removing one hydrogen atom, and a divalent aromatic heterocycle is an atomic group remaining after removing two hydrogen atoms. The number of carbon atoms in the aromatic heterocycle, not including the number of carbon atoms of the substituent, is usually 2 to 60, preferably 4 to 20.

[0017] Here, "aromatic heterocyclic compound" refers to compounds in which the heterocycle itself exhibits aromaticity, such as oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzosilole, dibenzophosphole, etc., and compounds in which an aromatic ring is condensed with a heterocycle, even if the heterocycle itself does not exhibit aromaticity, such as phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, benzopyran, etc. The aromatic heterocyclic compound is preferably a compound in which the heterocycle itself exhibits aromaticity.

[0018] In the structural unit (Aa), the aromatic heterocycle is preferably a nitrogen-containing aromatic heterocycle, more preferably a carbazole ring. The structural unit (Aa) is preferably a structural unit represented by formula (Aa-1).

[0019] [ka]

[0020] In formula (Aa-1), R 1 represents a hydrogen atom, a methyl group, or a hydroxymethyl group. R 2 ~R 9each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with an alkoxy group or an aryl group. X represents a single bond, an alkanediyl group having one or more carbon atoms, or a group represented by formula (V).

[0021] [ka]

[0022] In formula (V), l represents an integer of 0 or greater, and m represents an integer of 1 or greater. The group represented by formula (V) may be linear or branched.

[0023] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0024] Examples of alkyl groups having 1 to 20 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, and 2-ethylhexyl; and cyclic alkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. When an alkyl group has an alkoxy group or an aryl group, the number of carbon atoms in the alkyl group includes the carbon atoms in the alkoxy group or aryl group.

[0025] Examples of alkyl groups in which a hydrogen atom is substituted with an alkoxy group (alkoxyalkyl groups) include a methoxymethyl group, an ethoxymethyl group, and a methoxyethyl group.

[0026] Examples of alkyl groups in which a hydrogen atom is substituted with an aryl group (aralkyl groups) include benzyl groups, (2-methylphenyl)methyl groups, (3-methylphenyl)methyl groups, (4-methylphenyl)methyl groups, (2,4-dimethylphenyl)methyl groups, (ethylphenyl)methyl groups, and naphthylmethyl groups.

[0027] Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, and a triphenyl group (an o-terphenyl group, an m-terphenyl group, and a p-terphenyl group).

[0028] Examples of alkanediyl groups having one or more carbon atoms include a methanediyl (methylene) group, an ethanediyl (ethylene) group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.

[0029] Examples of unsaturated compounds that provide the structural unit (Aa) include 9-vinylcarbazole, 9-allylcarbazole, 9-(meth)acryloylcarbazole, 2-(9-carbazolyl)ethyl (meth)acrylate, 2-(9-carbazolyl)ethoxyethyl (meth)acrylate, 2-(9-carbazolyl)-2-methylethyl (meth)acrylate, and 2-(9-carbazolyl)-1-methylethyl (meth)acrylate. Among these, the unsaturated compound that provides the structural unit (Aa) is preferably 9-vinylcarbazole, 9-allylcarbazole, or 2-(9-carbazolyl)ethyl (meth)acrylate.

[0030] (Structural unit (Ab)) By including the structural unit (Ab), the resin (A) can improve the solvent resistance of the cured film obtained by heating at a low temperature.

[0031] An example of the structural unit (Ab) is a structural unit represented by the formula (Abx).

[0032] [ka]

[0033] In the formula (Abx), R 21 and R 22 each independently represents a hydrogen atom or a methyl group. R 25 represents an alkanediyl group having 1 to 20 carbon atoms, and one -CH2- contained in the alkanediyl group may be substituted with -O- or -CO-.

[0034] Examples of the alkanediyl group include a straight-chain alkanediyl group, a branched-chain alkanediyl group, a cyclic alkanediyl group, and groups formed by combining these groups.

[0035] Examples of linear alkanediyl groups include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl groups.

[0036] Examples of branched alkanediyl groups include ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, and 2-methyloctane-1,8-diyl groups.

[0037] Examples of cyclic alkanediyl groups include cycloalkanediyl groups such as cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-1,5-diyl, and polycyclic divalent alicyclic hydrocarbon groups such as norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl, and adamantane-2,6-diyl.

[0038] Examples of groups that combine a linear alkanediyl group and a cyclic alkanediyl group include groups of the following formulae (where * represents a bond).

[0039] [ka]

[0040] R 25 is preferably an alkanediyl group having 4 to 18 carbon atoms, more preferably an alkanediyl group having 4 to 10 carbon atoms, and even more preferably an alkanediyl group having 6 to 9 carbon atoms.

[0041] The structural unit represented by formula (Abx) is preferably R 25 It is a structural unit in which one of the -CH2- groups contained in the alkanediyl group in the formula (Abx) is replaced with -O-. Specific examples of the structural unit represented by formula (Ab-1), the structural unit represented by formula (Ab-21), and the structural unit represented by formula (Ab-22) are mentioned.

[0042] The structural unit represented by formula (Ab-1) can be prepared, for example, by referring to the method for preparing chemical structure (1) described in JP-A-2015-172117.

[0043] [ka]

[0044] In formula (Ab-1), R21 and R 22 each independently represents a hydrogen atom or a methyl group. R 23 and R 24 and each independently represent an alkanediyl group.

[0045] R 23 and R 24 The combination is preferably an alkanediyl group having 1 to 8 carbon atoms and an alkanediyl group having 1 to 8 carbon atoms, more preferably an alkanediyl group having 1 to 3 carbon atoms and a straight-chain alkanediyl group having 4 to 10 carbon atoms, and even more preferably a methylene group and a straight-chain alkanediyl group having 4 to 8 carbon atoms.

[0046] The structural unit represented by formula (Ab-1) is preferably a structural unit represented by formula (Ab-11) or a structural unit represented by formula (Ab-12). The structural unit represented by formula (Ab-11) is a structural unit represented by formula (Ab-1) where R 23 is a methylene group, and R 24 is a hexane-1,4-diyl group. The structural unit represented by formula (Ab-12) is a structural unit represented by formula (Ab-1) 23 is a hexane-1,4-diyl group, and R 24 is a methylene group.

[0047] [ka]

[0048] The structural unit represented by formula (Ab-21) and the structural unit represented by formula (Ab-22) can be prepared, for example, by referring to the method for preparing chemical structure (1) described in JP-A-2015-172117.

[0049] [ka]

[0050] In formula (Ab-21) and formula (Ab-22), R27 and R 28 each independently represents a hydrogen atom or a methyl group. R 26 represents an alkanediyl group having 1 to 4 carbon atoms. Ring W represents a cycloalkanediyl group having 5 to 7 carbon atoms.

[0051] R 26 is preferably a methylene group. Ring W is preferably a cyclohexanediyl group, more preferably a cyclohexane-1,4-diyl group.

[0052] The structural unit represented by formula (Ab-21) and the structural unit represented by formula (Ab-22) are preferably a structural unit represented by formula (Ab-21a) or a structural unit represented by formula (Ab-22a).

[0053] [ka]

[0054] The structural unit (Ab) can typically be obtained by adding a compound having an α,β-unsaturated carbonyl group to the structural unit (Ab') of the copolymer having a carboxy group. Alternatively, it can also be obtained by reacting a structural unit of the copolymer having an epoxy group with (meth)acrylic acid. The structural unit (Ab') is a type of structural unit (Ac) described below.

[0055] The compound having an α,β-unsaturated carbonyl group is not particularly limited as long as it can react with the carboxylic acid contained in the structural unit (Ab'). Examples of the compound having an α,β-unsaturated carbonyl group include (meth)acrylate (Ab'') having an epoxy group.

[0056] The (meth)acrylate (Ab'') having an epoxy group may have, for example, an aliphatic epoxy group. Here, the aliphatic epoxy group means a group in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized.

[0057] The structural unit (Ab) can be obtained, for example, by reacting 4-hydroxybutyl acrylate glycidyl ether with a (meth)acrylic structural unit having a carboxy group, or by reacting 4-hydroxybutyl acrylate glycidyl ether with a (meth)acrylic structural unit having an epoxy group. The structural unit (Ab) can also be obtained, for example, by reacting 5-hydroxypentyl acrylate glycidyl ether or 6-hydroxyhexyl acrylate glycidyl ether with a (meth)acrylic structural unit having a carboxy group or a (meth)acrylic structural unit having an epoxy group.

[0058] (Structural unit (Ac)) The structural unit (Ac) is a structural unit derived from an unsaturated compound having an acid group. Examples of the acid group include a carboxy group, a sulfo group, and a phenolic hydroxy group. The carboxy group may be an anhydride.

[0059] The structural unit (Ac) can be obtained by copolymerizing an unsaturated compound having an acid group as a monomer. Alternatively, it can also be obtained by reacting another structural unit (Ac') with a compound (Ac'') having an acid group.

[0060] The unsaturated compound having an acid group is preferably an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride.

[0061] Specific examples of the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride include: (Meth)acrylic acid, crotonic acid, vinylbenzoic acid, methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, α-(hydroxymethyl)(meth)acrylic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene; Unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (himic anhydride); Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids, such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate; unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)(meth)acrylic acid; and the like.

[0062] Of these, the unsaturated compound having an acid group is (meth)acrylic acid or maleic anhydride from the viewpoint of copolymerization reactivity and solubility in an alkaline aqueous solution.

[0063] (Structural unit (Ad)) The structural unit (Ad) is a structural unit different from the structural units (Aa), (Ab), and (Ac).

[0064] Specific examples of the monomer that provides the structural unit (Ad) include: (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate; alkyl acrylate esters such as methyl acrylate and isopropyl acrylate; Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 (meth)acrylic acid esters such as ]decan-8-yl(meth)acrylate (sometimes referred to as dicyclopentanyl(meth)acrylate in the technical field by the common name), dicyclopentanyloxyethyl(meth)acrylate, isobornyl(meth)acrylate, phenyl(meth)acrylate, benzyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, and 2-hydroxypropyl(meth)acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2 .2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[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, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene ]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2 Bicyclounsaturated compounds such as 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene anhydride (himic anhydride), 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide; styrene compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; Acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene; and the like.

[0065] (Proportion of each structural unit) The copolymer contains structural units (Aa), (Ab), and (Ac), and may further contain structural unit (Ad). The ratio of each structural unit, expressed as a mole fraction relative to the total number of moles of the structural units constituting the copolymer, is preferably in the following range: Structural unit (Aa): 1 to 90 mol%, Structural unit (Ab): 1 to 30 mol %, Structural unit (Ac): 1 to 30 mol %, Structural unit (Ad): 0 to 50 mol %.

[0066] Copolymers containing each structural unit can be produced, for example, in accordance with the method described in the literature "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and the references cited in said literature.

[0067] A copolymer containing each structural unit can be produced, for example, through a two-stage process. Specifically, a compound that provides the structural unit (Aa) and the structural unit (Ac), a compound that provides the structural unit (Ab') having a carboxy group, a polymerization initiator, and a solvent are charged into a reaction vessel, and oxygen is replaced with nitrogen. By stirring, heating (e.g., 50 to 140°C), and keeping the temperature (e.g., 1 to 10 hours) in the absence of oxygen, a copolymer containing the structural unit (Aa), the structural unit (Ab') having a carboxy group, and the structural unit (Ac) can be obtained. Thereafter, the nitrogen in the reaction vessel is replaced with oxygen, and a (meth)acrylate (Ab'') having an epoxy group, a reaction catalyst, a polymerization inhibitor, etc. are added to the reaction vessel, followed by stirring, heating (for example, 60 to 130°C), and keeping the temperature (for example, for 1 to 10 hours). This causes the (meth)acrylate (Ab'') having an epoxy group to react with the structural unit (Ab') having a carboxy group, thereby deriving the structural unit (Ab), and thus a copolymer having the structural unit (Aa), the structural unit (Ab), and the structural unit (Ac) is obtained.

[0068] The obtained copolymer may be used as a solution after the reaction as it is, or may be used as a concentrated or diluted solution, or may be extracted as a solid by a method such as reprecipitation and then dissolved in a solvent again for use.

[0069] When a copolymer further containing the structural unit (Ad) is produced, it can be produced by further adding a compound that provides the structural unit (Ad) in addition to the compounds that provide the structural unit (Aa) and the structural unit (Ac) and the compound that provides the structural unit (Ab') in the above step.

[0070] In the above, when the structural unit (Ac) has a carboxy group, the structural unit (Ab) can be obtained by reacting the structural unit (Ac) with a (meth)acrylate (Ab'') having an epoxy group.

[0071] The weight average molecular weight of the resin (A) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, and even more preferably 5,000 to 20,000.

[0072] A curable resin composition containing a resin (A) having a weight-average molecular weight within the above range tends to have good coatability when applied, is less likely to suffer film loss during development, and tends to have good removability of uncured portions during development.

[0073] The dispersity of the resin (A) [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the dispersity is within the above range, the curable resin composition containing this as a binder resin tends to have excellent developability.

[0074] The acid value of the resin (A) is preferably 70 to 150 mg-KOH / g, more preferably 75 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by titration with an aqueous potassium hydroxide solution.

[0075] A cured film formed from a curable resin composition containing resin (A) can exhibit excellent solvent resistance even when the temperature in the heating step after exposure (so-called post-baking step) during production of the cured film is 200° C. or lower or 150° C. or lower. The temperature in the post-baking step is preferably 70° C. or higher, more preferably 80° C. or higher.

[0076] <Polymerizable compound (B)> The polymerizable compound (B) is not particularly limited as long as it is a compound that can be polymerized by an active radical, an acid, etc. generated from the polymerization initiator (C) by light or heat. The polymerizable compound (B) is preferably a (meth)acryloyl compound having a (meth)acryloyl group.

[0077] Examples of the polymerizable compound (B) include a polymerizable compound having a fused ring (hereinafter, sometimes referred to as "polymerizable compound (B1)") and a polymerizable compound other than the polymerizable compound (B1) (hereinafter, sometimes referred to as "polymerizable compound (B2)"). Here, the fused ring refers to a ring formed by two or more rings sharing one side of each ring. The polymerizable compound (B) may be in an embodiment containing the polymerizable compound (B1). When the polymerizable compound (B) contains the polymerizable compound (B1), the amount of polymer particles (D) used to obtain the desired light diffusion properties tends to be reduced. On the other hand, the polymerizable compound (B) may be in an embodiment not containing the polymerizable compound (B1).

[0078] (Polymerizable compound (B1)) The polymerizable compound (B1) is a polymerizable compound having a fused ring. The fused ring is preferably a fused polycyclic aromatic ring. Here, the fused polycyclic aromatic ring refers to a ring in which two or more aromatic rings are fused. Examples of the fused polycyclic aromatic ring include fused polycyclic aromatic hydrocarbon rings such as a fluorene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring; and fused polycyclic aromatic heterocycles such as a quinoline ring, a quinoxaline ring, a benzofuran ring, a benzimidazole ring, a benzothiophene ring, and a carbazole ring. The fused polycyclic aromatic ring may have a substituent. The polymerizable compound (B1) is preferably a compound having a fused polycyclic aromatic hydrocarbon ring, more preferably a compound having a fluorene ring.

[0079] Examples of compounds having a fluorene ring include compounds represented by formula (VI).

[0080] [ka]

[0081] In formula (VI), L 1 and L 2each independently represents a single bond or an alkanediyl group having 1 to 16 carbon atoms which may have a substituent, and -CH2- contained in the alkanediyl group may be substituted with -O-, provided that the -CH2- group to which -O- is bonded is not substituted with -O-. R 11 and R 12 each independently represents a hydrogen atom or a methyl group.

[0082] The compound of formula (VI) is preferably a compound of formula (VIa).

[0083] [ka]

[0084] In formula (VIa), L 1a and L 2a each independently represents an alkanediyl group having 1 to 6 carbon atoms which may have a substituent. m and n each independently represent an integer of 0 to 8, provided that m+n is 0 to 16. When m and n are each 2 or more, multiple L 2a and L 2b may be the same or different. 2a and n L 2b The total number of carbon atoms therein is 0 to 30. R 11a and R 12a each independently represents a hydrogen atom or a methyl group.

[0085] (Polymerizable compound (B2)) Examples of the polymerizable compound (B2) include (meth)acryloyl compounds having a (meth)acryloyl group other than the polymerizable compound (B1).

[0086] Examples of (meth)acrylic compounds having one (meth)acryloyl group include (meth)acrylic acid alkyl esters, phenoxylated polyethylene glycol esters of (meth)acrylic acid, alkoxylated polyethylene glycol esters of (meth)acrylic acid, isobornyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

[0087] Examples of the (meth)acrylic compound having two (meth)acryloyl groups include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bis(acryloyloxyethyl)ether of bisphenol A, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, ethylene oxide-modified neopentyl glycol di(meth)acrylate, and 3-methylpentanediol di(meth)acrylate.

[0088] Examples of (meth)acrylic compounds having three or more (meth)acryloyl groups include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol poly(meth)acrylate (e.g., pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate), dipentaerythritol poly(meth)acrylate (e.g., dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate), tripentaerythritol Trititol poly(meth)acrylate (e.g., tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate), tetrapentaerythritol poly(meth)acrylate (e.g., tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate), tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene oxide-modified glycerin tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tris(meth)acrylate), (Meth)acrylate, ethylene oxide modified pentaerythritol poly(meth)acrylate (e.g., ethylene oxide modified pentaerythritol tri(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate), ethylene oxide modified dipentaerythritol poly(meth)acrylate (e.g., ethylene oxide modified dipentaerythritol penta(meth)acrylate, ethylene oxide modified dipentaerythritol hexa(meth)acrylate), propylene oxide modified glycerin tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified pentaerythritol poly(meth)acrylate (e.g., propylene oxide-modified pentaerythritol tri(meth)acrylate, propylene oxide-modified pentaerythritol tetra(meth)acrylate), propylene oxide-modified dipentaerythritol poly(meth)acrylate (e.g., propylene oxide-modified dipentaerythritol penta(meth)acrylate,propylene oxide-modified dipentaerythritol hexa(meth)acrylate), caprolactone-modified pentaerythritol poly(meth)acrylate (e.g., caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate), caprolactone-modified dipentaerythritol poly(meth)acrylate (e.g., caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate).

[0089] The polymerizable compound (B2) preferably contains a (meth)acrylic compound having three or more (meth)acryloyl groups, and more preferably contains ethylene oxide-modified glycerin tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, or ethylene glycol-modified dipentaerythritol hexa(meth)acrylate.

[0090] The total content of the resin (A) and the polymerizable compound (B) is preferably 40 to 98% by mass, more preferably 50 to 96% by mass, based on the total amount of solids in the curable resin composition. When the total content of the resin (A) and the polymerizable compound (B) is within the above range, the hardness of the cured film tends to be further improved and the refractive index tends to be higher. In this specification, the solid content of the curable resin composition means the total amount of components excluding the solvent from the curable resin composition. The total amount of solids in the curable resin composition and the content of each component relative to the total amount can be measured by known analytical means, such as liquid chromatography or gas chromatography.

[0091] The content of resin (A) is preferably 50 to 98 parts by mass, more preferably 60 to 95 parts by mass, per 100 parts by mass of the total of resin (A) and polymerizable compound (B). When the content of resin (A) is within the above range, the hardness of the cured film tends to be further improved.

[0092] The content of the polymerizable compound (B) is preferably 2 to 50 parts by mass, more preferably 5 to 40 parts by mass, per 100 parts by mass of the total of the resin (A) and the polymerizable compound (B). When the content of the polymerizable compound (B) is within the above range, the hardness of the cured film tends to be further improved.

[0093] <Polymerization initiator (C)> The polymerization initiator (C) is not particularly limited as long as it is a compound that generates active radicals, acids, etc. under the action of light or heat and can initiate polymerization of the polymerizable compound (B), and known polymerization initiators can be used. The polymerization initiator (C) is preferably at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds, and more preferably an O-acyloxime compound. The use of these polymerization initiators tends to result in high sensitivity and high transmittance in the visible light region.

[0094] An O-acyloxime compound is a compound having a partial structure represented by formula (C1). Hereinafter, * represents a bond.

[0095] [ka]

[0096] Examples of the O-acyloxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, and N-acetoxy -1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure OXE01, Irgacure OXE02, Irgacure OXE03 (all manufactured by BASF Ltd.), PBG-327 (N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arcles N-1919, Adeka Arcles NCI-831, Adeka Arcles NCI-930, Adeka Optomer N-1919 (all manufactured by ADEKA Corporation) may also be used.

[0097] The alkylphenone compound is a compound having a partial structure represented by formula (C2-1) or a partial structure represented by formula (C2-2). In these partial structures, the benzene ring may have a substituent.

[0098] [ka]

[0099] Examples of compounds having a partial structure represented by formula (C2-1) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (all manufactured by BASF Ltd.) may also be used. Furthermore, polymerization initiators having a chain transferable group, as described in JP-A-2002-544205, may also be used.

[0100] Examples of compounds having a partial structure represented by formula (C2-2) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal. From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (C2-1).

[0101] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0102] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure 819 (manufactured by BASF Japan Ltd.) may also be used.

[0103] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913).

[0104] Further examples of the polymerization initiator (C) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These can be used in combination with the polymerization initiator aid (F) described below (especially an amine compound).

[0105] An acid generator can also be used as the polymerization initiator (C). Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate, as well as nitrobenzyl tosylate and benzoin tosylate.

[0106] The content of the polymerization initiator (C) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 8 parts by mass, relative to 100 parts by mass of the total amount of the resin (A) and the polymerizable compound (B). When the content of the polymerization initiator (C) is within the above range, the curable resin composition has high sensitivity, and the strength and surface smoothness of the cured film formed using the curable resin composition tend to be good.

[0107] <Polymer particles (D)> The curable resin composition contains polymer particles (D). By containing the polymer particles (D) in the curable resin composition, the light diffusion properties of the resulting cured film can be improved. The polymer particles (D) are preferably (meth)acrylic resin particles.

[0108] The (meth)acrylic resin particles are fine particle components containing a (meth)acrylic resin as a main component. The type of (meth)acrylic resin constituting the (meth)acrylic resin particles is not particularly limited, and known (meth)acrylic resins can be used. Examples of the (meth)acrylic resin include polymers of (meth)acrylic acid esters. Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, hydroxyalkyl (meth)acrylate (number of carbon atoms in the alkyl group: for example, 2 to 10), and glycidyl (meth)acrylate.

[0109] The (meth)acrylic resin may be a homopolymer or a copolymer. When the (meth)acrylic resin is a copolymer, the (meth)acrylic resin may be a copolymer containing two or more (meth)acrylic acid esters, or may be a copolymer of a (meth)acrylic ester and a polymerizable monomer other than the (meth)acrylic ester. Examples of polymerizable monomers other than the (meth)acrylic ester include styrene, α-methylstyrene, maleic anhydride, (meth)acrylonitrile, vinyl acetate, vinyl chloride, vinylpyrrolidone, and vinylpyridine.

[0110] The average particle size of the polymer particles (D) is preferably 100 to 2300 nm, more preferably 300 to 1500 nm, and even more preferably 500 to 1200 nm.

[0111] In this specification, the average particle size means the particle size at 50% of the integrated value in the particle size distribution determined by a laser diffraction / scattering method.

[0112] The content of the polymer particles (D) is preferably 1 to 100 parts by mass, more preferably 3 to 80 parts by mass, per 100 parts by mass of the total of the resin (A) and the polymerizable compound (B). When the content of the polymer particles (D) is within the above range, the desired light scattering properties can be imparted to the obtained cured film, and a decrease in the coatability during production of the cured film tends to be suppressed.

[0113] <Solvent (E)> The solvent (E) is not particularly limited, and examples thereof include solvents commonly used in the art, such as ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule but not -O-, -CO-, or -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

[0114] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0115] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methylanisole.

[0116] Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methyl ...propionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl Examples of the alkyl ether acetate include ethyl 2-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0117] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0118] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0119] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0120] Among these, from the viewpoints of coatability and drying property, the solvent (F) is preferably a solvent having a boiling point at 1 atmosphere (atm) of 100 to 200° C. Such a solvent is preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol ethyl methyl ether, cyclohexanone, methoxybutanol, or methoxybutyl acetate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, methoxybutanol, or methoxybutyl acetate.

[0121] The content of the solvent (E) is preferably 40 to 95 mass%, more preferably 50 to 90 mass%, based on the total amount of the curable resin composition. In other words, the content of the solid content of the curable resin composition is preferably 5 to 60 mass%, more preferably 10 to 50 mass%, based on the total amount of the curable resin composition.

[0122] <Polymerization initiator aid (F)> The polymerization initiation aid (F) is a compound used together with the polymerization initiator (D) to promote the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D), or is a sensitizer.

[0123] Examples of the polymerization initiation aid (F) include thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0124] Examples of the thiazoline compound include compounds represented by formulae (F1-1) to (F1-3) and compounds described in JP-A No. 2008-65319.

[0125] [ka]

[0126] Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, among which 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.

[0127] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

[0128] Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0129] Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0130] The content of the polymerization initiation aid (F) is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 10 parts by mass, relative to 100 parts by mass of the total content of the alkali-soluble resin (A) and the polymerizable compound (C). When the amount of the polymerization initiation aid (F) is within the above range, there is a tendency for further high sensitivity in pattern formation.

[0131] <Other ingredients> The curable resin composition may contain additives known in the technical field, such as a leveling agent, an antioxidant, a filler, other polymer compounds, an ultraviolet absorber, a chain transfer agent, and an adhesion promoter, as needed.

[0132] The curable resin composition preferably satisfies the following formula (1): When the curable resin composition satisfies the following formula (1), the light diffusibility of the resulting cured film can be further improved. 0<[(x+y)×z]≦26.0 (1)

[0133] In formula (1), x represents the ratio (unit: mol / g) of the content (unit: parts by mass) of the polymer containing a structural unit having an aromatic heterocycle per 1 mol of the aromatic heterocycle, when the total mass of the resin (A) and the polymerizable compound (B) is taken as 100, or the sum thereof.

[0134] In formula (1), y represents the ratio (unit: mol / g) of the content (unit: parts by mass) of the prepolymerizable compound relative to the mass (unit: g) of the polymerizable compound having a fused ring per 1 mole of the fused ring, when the total mass of the resin (A) and the polymerizable compound (B) is taken as 100, or the sum thereof.

[0135] z represents the content (unit: parts by mass) of the polymer particles (D) when the total of the resin (A) and the polymerizable compound (B) is taken as 100 mass.

[0136] When two or more polymers containing a structural unit having an aromatic heterocycle are used in combination as resin (A), a predetermined ratio can be calculated for each polymer, and the sum of these ratios can be defined as x. For example, when two polymers containing a structural unit having an aromatic heterocycle, polymer (A1) and polymer (A2), are used, x is the sum of the ratio of the content (unit: parts by mass) of polymer (A1) to the mass (unit: g) of polymer (A1) per 1 mol of aromatic heterocycle, when the total of resin (A) and polymerizable compound (B) is taken as 100 mass, and the ratio of the content (unit: parts by mass) of polymer (A2) to the mass (unit: g) of polymer (A2) per 1 mol of aromatic heterocycle, when the total of resin (A) and polymerizable compound (B) is taken as 100 mass.

[0137] When two or more polymerizable compounds having a fused ring are used in combination as the polymerizable compound (B), a predetermined ratio can be calculated for each polymerizable compound, and the sum of these ratios can be defined as y. For example, when two polymerizable compounds having a fused ring, a polymerizable compound (B1) having a fused ring and a polymerizable compound (B2) having a fused ring, are used as the polymerizable compounds having a fused ring, y is the sum of the ratio (mol / g) of the content (unit: parts by mass) of (B1) to the mass (unit: g) of the polymerizable compound (B1) per 1 mole of the fused ring, when the total mass of the resin (A) and the polymerizable compound (B) is 100, and the ratio (mol / g) of the content (unit: parts by mass) of (B2) to the mass (unit: g) of the polymerizable compound (B2) per 1 mole of the fused ring, when the total mass of the resin (A) and the polymerizable compound (B) is 100.

[0138] [(x+y)×z] is greater than 0 and less than or equal to 26.0, and may be 0.5 or more, 1.0 or more, 2.0 or more, 4.0 or more, 6.0 or more, 8.0 or more, 10.0 or more, 12.0 or more, 14.0 or more, 16.0 or more, or 18.0 or more, or may be 24.0 or less, 22.0 or less, 20.0 or less, 18.0 or less, 16.0 or less, 14.0 or less, 12.0 or less, 10.0 or less, 8.0 or less, or 6.0 or less.

[0139] [Method for producing curable resin composition] The curable resin composition can be produced by mixing the resin (A), the polymerizable compound (B), the polymerization initiator (C), the polymer particles (D), and, optionally, the solvent (E), the polymerization initiator aid (F), and other components by a known method. After mixing the components, the curable resin composition is preferably filtered through a filter having a pore size of about 0.01 to 10 μm.

[0140] [Cured film (patterned cured film) and its manufacturing method] Methods for producing a cured film or a patterned cured film (patterned cured film) from the curable resin composition of this embodiment include photolithography, inkjet printing, and printing. Among these, the method for producing a patterned cured film is preferably photolithography. The photolithography method is a method in which the curable resin composition is applied to a substrate, dried to form a coating film, and the coating film is exposed to light through a photomask and developed. In the photolithography method, a cured film (non-patterned cured film) that is a cured product of the coating film can be formed by not using a photomask during exposure and / or not developing.

[0141] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and silica-coated soda lime glass; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon substrates; and substrates having a thin film of aluminum, silver, silver / copper / palladium alloy, etc. formed on the substrate. These substrates may have other cured films, resin films, transistors, circuits, etc. formed on them.

[0142] The thickness of the cured film is not particularly limited and can be adjusted appropriately depending on the purpose, application, etc. The thickness of the cured film may be, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

[0143] The haze of the cured film may be 1% or more, 3% or more, 5% or more, 7% or more, 10% or more, 15% or more, 20% or more, 25% or more, or 30% or more, and may be 80% or less, 75% or less, or 70% or less, calculated based on a thickness of 2 μm. The haze of the cured film can be measured using a haze meter.

[0144] The pencil hardness of the cured film is preferably H or higher, more preferably 2H or higher. The pencil hardness of the cured film can be measured using a Tribogear reciprocating abrasion tester (TYPE: 30, manufactured by HEIDON) in accordance with the pencil hardness test specified in JIS K5600-5-4:1999 "General test methods for paints - Part 5: Mechanical properties of coating films - Section 4: Scratch hardness (pencil method)" under the following measurement conditions. <Measurement conditions> Load 500g ·Speed ​​40mm / s

[0145] The formation of each cured film by photolithography can be carried out using known or conventional equipment, conditions, etc. The formation of each cured film by photolithography can be carried out, for example, as follows.

[0146] First, the curable resin composition is applied onto a substrate, and then dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as solvents, thereby obtaining a smooth coating film.

[0147] Examples of coating methods include spin coating, slit coating, and slit and spin coating. When drying by heating, the temperature is preferably 30 to 120°C, and more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When drying under reduced pressure, it is preferably performed under a pressure of 50 to 150 Pa at a temperature of 20 to 25°C.

[0148] The thickness of the coating film is not particularly limited and can be appropriately selected depending on the desired thickness of the cured film.

[0149] The coating film is then exposed to light through a photomask to form a desired patterned cured film. The pattern of the photomask is not particularly limited, and any pattern appropriate for the intended use can be used.

[0150] The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. The light source used for exposure may be, for example, one that cuts out light of less than 350 nm using a filter that cuts out this wavelength range, or one that selectively extracts light of around 436 nm, around 408 nm, and around 365 nm using a bandpass filter that extracts these wavelength ranges. Specific examples of light sources used for exposure include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.

[0151] For exposure, it is preferable to use an exposure device such as a mask aligner or stepper, since this allows parallel light to be uniformly irradiated onto the entire exposure surface and allows accurate alignment of the photomask with the substrate on which the coating film is formed.

[0152] The exposed coating film is brought into contact with a developer and developed to form a patterned cured film on the substrate. By development, the unexposed areas of the cured film are dissolved and removed in the developer, leaving the exposed areas of the cured film. Examples of the developer include aqueous solutions (aqueous developers) containing alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of the alkaline compound in these aqueous developers is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The developer may further contain a surfactant.

[0153] Examples of the development method include a puddle method, a dipping method, a spray method, etc. During development, the substrate may be tilted at any angle. After development, it is preferable to wash the obtained patterned cured film with water.

[0154] The obtained patterned cured film is preferably post-baked. The post-baking temperature is preferably 50 to 250° C., more preferably 70 to 235° C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

[0155] [Display device] The display device of this embodiment includes a cured film, a patterned cured film, and the like.

[0156] Examples of the display device include a liquid crystal display device, an electroluminescence display device, and a plasma display device. [Example]

[0157] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples, and can be practiced with appropriate modifications within the scope of the above and below spirit, all of which are within the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass." In the following examples, "room temperature" means 18 to 24°C.

[0158] The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC under the following conditions. Apparatus: HLC-8120GPC (Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40℃ Solvent: tetrahydrofuran Flow rate: 1.0mL / min Solid concentration of the analytical sample: 0.001 to 0.01% by mass Injection volume: 50μL Detector: RI Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0159] The ratio of the weight average molecular weight and the number average molecular weight (Mw / Mn) calculated in terms of polystyrene obtained above was taken as the dispersity.

[0160] (Synthesis Example 1) <Synthesis of Copolymer (A-1)> A flask equipped with a reflux condenser, a dropping funnel, and a stirrer was purged with nitrogen by flowing an appropriate amount of nitrogen, and 300 parts by weight of propylene glycol monomethyl ether acetate was added and heated to 100°C with stirring. Next, a mixed solution of 38 parts by weight of acrylic acid, 150 parts by weight of 9-vinylcarbazole, and 136 parts by weight of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Next, a mixed solution of 35 parts by weight of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 215 parts by weight of propylene glycol monomethyl ether acetate was added dropwise over 6 hours, and the mixture was then maintained at 100°C for 4 hours. The mixture was then changed to a mixed gas flow of 7% oxygen by volume and 93% nitrogen by volume, and 2 parts by mass of 4-methoxyphenol and 2 parts by mass of triphenylphosphine were added. A mixed solution of 12 parts by mass of 4-hydroxybutyl acrylate glycidyl ether and 110 parts by mass of propylene glycol monomethyl ether acetate was added dropwise over 4 hours, and the mixture was then maintained at 100°C for 15 hours to obtain a copolymer (A-1) solution. The resulting copolymer (A-1) solution had a Brookfield viscosity (23°C) of 15 mPas and a solids content of 21.4% by mass. The copolymer (A-1) had a weight-average molecular weight Mw of 6800 and a polydispersity of 1.96. The copolymer (A-1) has the following structural units:

[0161] [ka]

[0162] (Synthesis Example 2) <Synthesis of copolymer (a-1)> A flask equipped with a stirring blade, reflux condenser, thermometer, and dropping funnel was charged with 224 parts of propylene glycol monomethyl ether and heated to 90°C. A solution containing 170.3 parts of vinyl toluene, 87.4 parts of 2-(acetoacetoxy)ethyl methacrylate, 74.9 parts of methacrylic acid, 16.0 parts of azobis(isobutyronitrile), and 96.0 parts of propylene glycol monomethyl ether was continuously added dropwise to the flask using the dropping funnel. The temperature inside the flask was maintained at 90±1°C during the dropping of the mixed solution, and the dropping was completed after 3 hours. After the dropping was completed, the temperature inside the flask was maintained at 90±1°C for 6 hours. After the reaction, the reaction solution was cooled to below 40°C, and 0.4 parts of 4-methoxyphenol, 53.4 parts of 3,4-epoxycyclohexylmethyl acrylate, 15.0 parts of triphenylphosphine, and 262.5 parts of propylene glycol monomethyl ether were added. The temperature in the flask was raised to 110°C, and then an addition reaction was carried out at a temperature of 110±1°C to obtain a copolymer (a-1) solution. The solids content of the obtained copolymer (a-1) solution was 38.6% by mass. The weight-average molecular weight (Mw) of the copolymer (a-1) was 14,500, and the acid value (solids equivalent) was 89 mg-KOH / g. The copolymer (a-1) has the following structural units.

[0163] [ka]

[0164] (Examples 1 to 6 and Comparative Example 1) <Preparation of Curable Resin Composition> Resin (A), polymerizable compound (B), polymerization initiator (C), and polymer particles (D) were mixed in the proportions shown in Table 1 and filtered using a 4.5 μm PS (polysulfone) filter to obtain curable resin compositions of Examples 1 to 6 and Comparative Example 1. In Table 1, the number of parts of each component represents parts by mass converted into solid content.

[0165] The components shown in Table 1 are as follows: Resin (A) (polymer containing a structural unit having an aromatic heterocycle) (A-1) Copolymer (A-1) of Synthesis Example 1 Resin (a) (polymer not containing a structural unit having an aromatic heterocycle) (a-1) Copolymer (a-1) of Synthesis Example 2 ·Polymerizable compound (B) (B-1) A-9550 (dipentaerythritol polyacrylate (5-6 functional groups), manufactured by Shin-Nakamura Chemical Co., Ltd.) (B-2) EA-0300 (fluorene-based acrylate (bifunctional), manufactured by Osaka Gas Chemicals Co., Ltd.) Polymerization initiator (C) (C-1) N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure® OXE 01, manufactured by BASF, oxime compound) Polymer particles (D) (D-1) BMSA-18GN (acrylic resin particles, manufactured by Sekisui Plastics Co., Ltd., average particle diameter 800 nm) (D-2) MV-1002 (acrylic resin particles, manufactured by Nippon Shokubai Co., Ltd., average particle diameter 2400 nm) Solvent (E) (E-1) Propylene glycol monomethyl ether acetate

[0166] <Calculation of [(x+y)×z]> The ratio (mol / g) of the content of resin (A) (unit: parts by mass) when the total of resin (A) and polymerizable compound (B) is taken as 100 masses to the mass of resin (A) (unit: g) per mole of aromatic heterocycle was calculated and designated x. The ratio (mol / g) of the content of polymerizable compound having fused rings (unit: parts by mass) when the total of resin (A) and polymerizable compound (B) is taken as 100 masses to the mass of polymerizable compound having fused rings per mole of fused rings (unit: g) was calculated and designated y. The content (unit: parts by mass) of polymer particles (D) when the total of resin (A) and polymerizable compound (B) is taken as 100 masses was designated z. From these, [(x + y) × z] was calculated. The results are shown in Table 1.

[0167] <Preparation of cured film> The curable resin composition prepared above was applied by spin coating onto a 5 cm square glass substrate (Eagle 2000, manufactured by Corning Incorporated) and prebaked at 85°C for 2 minutes to form a coating film. After cooling, the substrate on which the coating film was formed was exposed to 100 mJ / cm 2 in air using an exposure machine (TME-150RSK, manufactured by Topcon Corporation). 2 The film was irradiated with light at an exposure dose of 100 μm (based on 365 nm). A photomask with a 100 μm line and space pattern was used. After irradiation, the coating film was immersed and developed in an aqueous developer containing 2.38 mass% of tetramethylammonium hydroxide at 23°C for 60 seconds, washed with water, and then post-baked in an oven at 85°C for 30 minutes to obtain a cured film. The film thickness of the resulting cured film was measured using a film thickness measuring device (DEKTAK3, manufactured by ULVAC, Inc.) and confirmed to be 3.0 μm.

[0168] <Haze measurement> The haze of the resulting cured film was measured using a haze meter HZ-2 (manufactured by Suga Test Instruments Co., Ltd.), and the haze converted into a thickness of 2 μm was calculated. The results are shown in Table 1.

[0169] <Pencil hardness measurement> The pencil hardness of the surface of the resulting cured film was measured using a Tribogear reciprocating abrasion tester (Type: 30, manufactured by HEIDON) in accordance with the pencil hardness test specified in JIS K5600-5-4:1999 "General test methods for coatings - Part 5: Mechanical properties of coating films - Section 4: Scratch hardness (pencil method)." The load used in the measurement was 500 g, and the speed was 40 mm / s. The results are shown in Table 1.

[0170] [Table 1]

[0171] As shown in Table 1, the cured films formed from the curable resin compositions of Examples 1 to 6 had sufficiently high haze and also sufficiently high pencil hardness. In contrast, the cured film formed from the curable resin composition of Comparative Example 1 had sufficiently high haze, but was inferior in pencil hardness to the cured films formed from the curable resin compositions of Examples 1 to 6. These results confirmed that the curable resin composition of the present disclosure can form a cured product with excellent light diffusibility and hardness.

Claims

1. The composition contains a resin (A), a polymerizable compound (B), a polymerization initiator (C), and polymer particles (D), The curable resin composition, wherein the resin (A) is a polymer containing a structural unit having an aromatic heterocycle.

2. The curable resin composition according to claim 1 , wherein the polymerizable compound (B) includes a polymerizable compound having a fused ring.

3. The curable resin composition according to claim 2, which satisfies the following formula (1): 0<[(x+y)×z]≦26.0 (1) [In formula (1), x represents the ratio (unit: mol / g) of the content (unit: parts by mass) of the polymer containing a structural unit having an aromatic heterocycle per 1 mol of the aromatic heterocycle, when the total mass of the resin (A) and the polymerizable compound (B) is taken as 100, or the sum thereof; y represents the ratio (unit: mol / g) of the content (unit: parts by mass) of the polymerizable compound having a fused ring per 1 mol of the fused ring, when the total mass of the resin (A) and the polymerizable compound (B) is taken as 100 mass, to the mass (unit: g) of the polymerizable compound having the fused ring, or the sum thereof; z represents the content (unit: parts by mass) of the polymer particles (D) when the total mass of the resin (A) and the polymerizable compound (B) is 100.

4. The curable resin composition according to claim 1 , wherein the aromatic heterocycle is a carbazole ring.

5. The curable resin composition according to claim 1, wherein the polymer particles (D) have an average particle size of 100 to 2300 nm.

6. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 5.

7. A display device comprising the cured film according to claim 6.

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