Curable composition and cured film

Abstract

The present invention relates to a curable composition comprising inorganic fine particles (A), a polymerizable compound (B), and a polymerization initiator (C), wherein the polymerizable compound (B) comprises a compound having an aromatic heterocyclic ring and one or two polymerizable groups selected from the group consisting of vinyl, 1-methylvinyl, allyl, methallyl, acryloyl, methacryloyl, vinyloxy, 1-methylvinyloxy, allyloxy, methallyloxy, acryloyloxy, and methacryloyloxy.

Description

Technical Field

[0001] The present invention relates to a curable composition and a cured film. Background Art

[0002] Organic electroluminescent devices are used in display devices, lighting devices, etc., and research has been conducted to control the refractive index to improve the efficiency of extracting light from the light-emitting layer. Patent Document 1 aims to provide a curable composition with a high refractive index, and discloses, for example, the following curable composition, which contains a polymerization initiator and a surfactant, and 45% by mass of zirconium oxide nanoparticles, 25% by mass of tricyclodecane dimethanol dimethacrylate as a ring structure multifunctional compound, 14% by mass of 1,9-nonanediol dimethacrylate as a non-ring structure multifunctional compound, and 10% by mass of isobutyl methacrylate as a monofunctional compound.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2017-61606 Summary of the invention

[0006] Problems to be solved by the invention

[0007] However, when a ring structure polyfunctional compound and a non-ring structure polyfunctional compound are combined, the curable composition may not be sufficiently cured.

[0008] An object of the present invention is to provide a curable composition having excellent curability.

[0009] Means for solving problems

[0010] The present invention that can solve the above-mentioned problems has the following configurations.

[0011] [1] A curable composition comprising inorganic fine particles (A), a polymerizable compound (B), and a polymerization initiator (C),

[0012] The polymerizable compound (B) contains a compound having an aromatic heterocyclic ring and one or two polymerizable groups selected from the group consisting of vinyl, 1-methylvinyl, allyl, methallyl, acryloyl, methacryloyl, vinyloxy, 1-methylvinyloxy, allyloxy, methallyloxy, acryloyloxy, and methacryloyloxy.

[0013] [2] The curable composition according to [1], wherein the polymerizable compound (B) is a compound represented by formula (B1b).

[0014] [Chemical formula 1]

[0015]

[0016] (Wherein, X is a nitrogen atom, an oxygen atom, or a sulfur atom.

[0017] When X is an oxygen atom or a sulfur atom, n is 0.

[0018] When X is a nitrogen atom, n is 1, R 1 It is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, a 1-methylvinyl group, an allyl group, a methallyl group, an acryloyl group, or a methacryloyl group.

[0019] R 2 ~R 9 is a hydrogen atom, a vinyl group, a 1-methylvinyl group, an allyl group, a methallyl group, an acryloyl group, a methacryloyl group, a vinyloxy group, a 1-methylvinyloxy group, an allyloxy group, a methallyloxy group, an acryloyloxy group, a methacryloyloxy group, an alkyl group having 1 to 20 carbon atoms, or a substituent, and R 2 ~R 9 Two adjacent groups in the above-mentioned groups may be bonded to each other to form an aromatic hydrocarbon ring, to which may be bonded a vinyl group, a 1-methylvinyl group, an allyl group, a methallyl group, an acryloyl group, a methacryloyl group, a vinyloxy group, a 1-methylvinyloxy group, an allyloxy group, a methallyloxy group, an acryloyloxy group, a methacryloyloxy group, an alkyl group having 1 to 20 carbon atoms, or a substituent group.

[0020] The alkyl group having 1 to 20 carbon atoms may be bonded with a vinyl group, 1-methylvinyl group, acryloyl group, methacryloyl group, vinyloxy group, 1-methylvinyloxy group, allyloxy group, methallyloxy group, acryloyloxy group, methacryloyloxy group or a substituent.

[0021] The aforementioned substituents are halogen atoms, hydroxyl groups, -NR a R b (R a and R b Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a nitro group, an alkoxy group having 1 to 10 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms.

[0022] The compound represented by formula (B1b) has one or two groups selected from the group consisting of vinyl, 1-methylvinyl, allyl, methallyl, acryloyl, methacryloyl, vinyloxy, 1-methylvinyloxy, allyloxy, methallyloxy, acryloyloxy, and methacryloyloxy.

[0023] [3] The curable composition according to [1] or [2], further comprising a polymerizable compound (BX2) that does not contain an aromatic heterocyclic ring.

[0024] [4] The curable composition according to any one of [1] to [3], wherein the content of the inorganic fine particles (A) in the curable composition is 20% by mass or more.

[0025] [5] A cured film formed from the curable composition according to any one of [1] to [4].

[0026] Effects of the Invention

[0027] According to the present invention, the curability of the curable composition can be improved. DETAILED DESCRIPTION

[0028] The present invention is a curable composition comprising inorganic fine particles (A), a polymerizable compound (B), and a polymerization initiator (C), characterized in that the composition comprises specific monomers as the polymerizable compound (B). With such a curable composition, the obtained film has excellent visible light transmittance and excellent curability.

[0029] <Inorganic fine particles (A)>

[0030] The inorganic particles (A) are preferably particles that do not have the ability to convert wavelengths to the visible light region, and preferably particles with a refractive index of 1.6 or more. The higher the refractive index of the inorganic particles (A), the higher the refractive index of the film obtained by the curable composition, and the efficiency of extracting light from the luminescent layer is improved. The refractive index is preferably 1.8 or more, more preferably 2.0 or more. In addition, the refractive index can be, for example, 3.5 or less, or 3.0 or less. The refractive index is the value at the D line of sodium.

[0031] The inorganic particles (A) include oxides, nitrides, etc. Specifically, TiO2 (titanium oxide; refractive index 2.3 to 2.7), Nb2O5 (niobium oxide; refractive index 2.3), Ta2O5 (tantalum oxide; refractive index 2.3), BN (boron nitride; refractive index 2.2), ZrO2 (zirconium oxide; refractive index 2.1), SnO2 (tin oxide; refractive index 2.0), ITO (tin-doped indium oxide; refractive index 2.0), Si3N4 (silicon nitride; refractive index 2.0), CeO2 (cerium oxide; refractive index 1.9 to 2.0 ), ZnO (zinc oxide; refractive index 1.9), Y2O3 (yttrium oxide; refractive index 1.9), ATO (antimony-doped tin oxide; refractive index 1.7-1.9), SbO5 (antimony oxide; refractive index 1.8), Al2O3 (aluminum oxide; refractive index 1.8), TiN (titanium nitride; refractive index 1.6), etc., preferably oxides of elements of Groups 3 to 5 and Groups 12 to 15 of the periodic table, or nitrides of elements of Group 4 of the periodic table, more preferably titanium oxide, zirconium oxide, aluminum oxide, niobium oxide, and silicon nitride, and further preferably titanium oxide and zirconium oxide. These inorganic fine particles (A) may be one kind or a combination of two or more kinds.

[0032] The volume average particle diameter of the inorganic particles (A) is, for example, less than 100 nm, preferably less than 50 nm, and more preferably less than 30 nm. The smaller the particle diameter, the more the visible light transmittance of the obtained film can be improved. The lower limit of the volume average particle diameter of the inorganic particles (A) is not particularly limited, for example, more than 0.1 nm, preferably more than 0.5 nm, and more preferably more than 1.0 nm.

[0033] In the curable composition, the content of the inorganic particles (A) is, for example, 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more. The higher the content of the inorganic particles (A), the higher the refractive index of the film obtained by the curable composition, and the efficiency of extracting light from the luminescent layer is improved. The content of the inorganic particles (A) is, for example, 80% by mass or less, preferably 70% by mass or less, and more preferably 60% by mass or less.

[0034] The inorganic fine particles (A) may be surface treated with a coupling agent. Examples of the coupling agent include silane coupling agents, zirconium coupling agents, titanium coupling agents, phosphorus coupling agents, etc. These may be used alone or in combination of two or more.

[0035] Examples of the silane coupling agent include γ-(meth)acryloxypropyldimethylmethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyldimethylmethoxysilane, phenylmethyldimethoxysilane, phenyldiethylmethoxysilane, phenylethyldimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane.

[0036] Examples of the zirconium coupling agent include tetrapropyl zirconate, tetrabutyl zirconate, tetrakis(triethanolamine)zirconate, tetraisopropyl zirconate, zirconium acetylacetonate, zirconium acetylacetonate butyrate, zirconium stearate, zirconium stearate butyrate, monoalkoxy zirconium aluminate, trialkoxy zirconium aluminate, and tetraalkoxy zirconium aluminate.

[0037] Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl tristearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryloyl isostearyl titanate, isopropyl tri(dodecyl)benzenesulfonyl titanate, isopropyl isostearyl diacryloyl titanate, isopropyl tri(dioctyl phosphate) titanate, and isopropyl triisostearate titanate.

[0038] Examples of the phosphorus coupling agent include isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetrakis(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl) phosphite titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)ethylene titanate, and acryloyloxyethylphthaloylethyl diethyl phosphate.

[0039] In addition, inorganic fine particles (A) can be included in the curable composition together with a dispersant. As a dispersant, any type of dispersant such as a nonionic, anionic, or cationic dispersant can also be used, preferably an anionic dispersant. As an anionic dispersant, a phosphate dispersant can be preferably used.

[0040] As the dispersant, commercially available products may be used, for example, DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 (BYK Chemie, GMBH), Solsperse 32000, Solsperse 36000, Solsperse 28000, Solsperse 20000, Solsperse 41000, and Solsperse 45000 (Lubrizol, Wickliffe, OH, USA).

[0041] Relative to 100 parts by mass of inorganic particles (A), the amount of dispersant is, for example, more than 1 part by mass, preferably more than 5 parts by mass, more preferably more than 10 parts by mass. The more the amount of dispersant, the more the dispersibility of inorganic particles (A) can be improved. In addition, relative to 100 parts by mass of inorganic particles (A), the amount of dispersant is, for example, less than 100 parts by mass, preferably less than 60 parts by mass, more preferably less than 40 parts by mass. The less the amount of dispersant, the more the refractive index of curable composition can be improved.

[0042] <Polymerizable compound (B)>

[0043] The polymerizable compound (B) contains a compound having an aromatic heterocycle (hereinafter, sometimes referred to as a polymerizable compound (B1)) and one or two polymerizable groups selected from the group consisting of a vinyl group, a 1-methylvinyl group, an allyl group, a methallyl group, an acryloyl group, a methacryloyl group, a vinyloxy group, a 1-methylvinyloxy group, an allyloxy group, a methallyloxy group, an acryloyloxy group, and a methacryloyloxy group (hereinafter, sometimes referred to as a polymerizable group (V)).

[0044] The number of the polymerizable group (V) contained in the polymerizable compound (B1) is preferably one.

[0045] The aromatic heterocyclic ring may be any of a nitrogen-containing aromatic heterocyclic ring, a sulfur-containing aromatic heterocyclic ring, and an oxygen-containing aromatic heterocyclic ring, and is preferably a pyrrole ring that may be fused with other rings, a thiophene ring that may be fused with other rings, a furan ring that may be fused with other rings, etc. In addition, a substituent or an alkyl group having 1 to 20 carbon atoms may be bonded to the pyrrole ring, thiophene ring, and furan ring that may be fused with other rings, and the alkyl group having 1 to 20 carbon atoms may be bonded to a substituent.

[0046] As the pyrrole ring that can be fused with other rings, for example, a pyrrole ring, an indole ring, an isoindole ring, a carbazole ring, a naphthopyrrole ring, a dinaphthopyrrole ring, etc. can be mentioned. As the thiophene ring that can be fused with other rings, a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a naphthothiophene ring, a dinaphthothiophene ring, etc. can be mentioned. As the furan ring that can be fused with other rings, a furan ring, a benzofuran ring, a dibenzofuran ring, a naphthofuran ring, a dinaphthofuran ring, etc. can be mentioned.

[0047] The alkyl group having 1 to 20 carbon atoms may be any of a linear group and a branched group. Specific examples of the linear or branched alkyl group include methyl, ethyl, propyl, isobutyl, butyl, tert-butyl, hexyl, heptyl, octyl, nonyl, decyl, heptadecyl, and undecyl groups. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 4 carbon atoms.

[0048] Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; -NR a R b (R a and R b each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; an alkoxycarbonyl group having 2 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; and the like.

[0049] The polymerizable compound (B1) is more preferably a compound represented by the formula (B1b) (hereinafter, sometimes referred to as compound (B1b)).

[0050] [Chemical formula 2]

[0051]

[0052] (Wherein, X is a nitrogen atom, an oxygen atom, or a sulfur atom.

[0053] When X is an oxygen atom or a sulfur atom, n is 0.

[0054] When X is a nitrogen atom, n is 1, R 1It is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, a 1-methylvinyl group, an allyl group, a methallyl group, an acryloyl group, or a methacryloyl group.

[0055] R 2 ~R 9 is a hydrogen atom, a vinyl group, a 1-methylvinyl group, an allyl group, a methallyl group, an acryloyl group, a methacryloyl group, a vinyloxy group, a 1-methylvinyloxy group, an allyloxy group, a methallyloxy group, an acryloyloxy group, a methacryloyloxy group, an alkyl group having 1 to 20 carbon atoms, or a substituent, and R 2 ~R 9 Two adjacent groups in the above-mentioned groups may be bonded to each other to form an aromatic hydrocarbon ring, to which may be bonded a vinyl group, a 1-methylvinyl group, an allyl group, a methallyl group, an acryloyl group, a methacryloyl group, a vinyloxy group, a 1-methylvinyloxy group, an allyloxy group, a methallyloxy group, an acryloyloxy group, a methacryloyloxy group, an alkyl group having 1 to 20 carbon atoms, or a substituent group.

[0056] The alkyl group having 1 to 20 carbon atoms may be bonded with a vinyl group, a 1-methylvinyl group, an acryloyl group, a methacryloyl group, a vinyloxy group, a 1-methylvinyloxy group, an allyloxy group, a methallyloxy group, an acryloyloxy group, a methacryloyloxy group, or a substituent.

[0057] The aforementioned substituents are halogen atoms, hydroxyl groups, -NR a R b (R a and R b Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a nitro group, an alkoxy group having 1 to 10 carbon atoms, or an alkoxycarbonyl group having 2 to 10 carbon atoms.

[0058] The compound represented by formula (B1b) has one or two groups selected from the group consisting of vinyl, 1-methylvinyl, allyl, methallyl, acryloyl, methacryloyl, vinyloxy, 1-methylvinyloxy, allyloxy, methallyloxy, acryloyloxy, and methacryloyloxy.

[0059] X is preferably a nitrogen atom or a sulfur atom.

[0060] Preferred: R 2 ~R 9 are all hydrogen atoms or polymerizable groups (V) (Form a); or, R 2 ~R 9 Two adjacent ones of the two are bonded to each other to form an aromatic hydrocarbon ring, and R 2 ~R 9The group not constituting the aromatic hydrocarbon ring is a hydrogen atom or a polymerizable group (V) (embodiment b).

[0061] As R 2 ~R 9 Examples of the aromatic hydrocarbon ring formed by bonding include a benzene ring, a naphthalene ring, and an anthracene ring.

[0062] Examples of the alkyl group having 1 to 20 carbon atoms constituting the compound (B1b) include the same alkyl groups as those constituting the polymerizable compound (B1). Examples of the substituent constituting the compound (B1b) include the same substituents as those constituting the polymerizable compound (B1).

[0063] The compound (B1b) has one or two groups selected from the group consisting of a vinyl group, an allyl group, an allyloxy group, an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group, and more preferably has one group selected from the group consisting of a vinyl group, an allyl group, an allyloxy group, an acryloyl group, an acryloyloxy group, and a methacryloyloxy group.

[0064] When X is a nitrogen atom, R 1 Preferably, it is vinyl, 1-methylvinyl, allyl, methallyl, acryloyl, methacryloyl, vinyloxy, 1-methylvinyloxy, allyloxy, methallyloxy, acryloyloxy, or methacryloyloxy,

[0065] When X is an oxygen atom or a sulfur atom, R 2 ~R 9 One or two of them are each independently vinyl, 1-methylvinyl, allyl, methallyl, acryloyl, methacryloyl, vinyloxy, 1-methylvinyloxy, allyloxy, methallyloxy, acryloyloxy, or methacryloyloxy.

[0066] The polymerizable compound (B1) is preferably a compound represented by formula (B1c-1) to (B1c-4) and (B1d-1) to (B1d-7), and more preferably a compound represented by formula (B1c-1) and (B1d-5).

[0067] [Chemical formula 3]

[0068]

[0069] [Chemical formula 4]

[0070]

[0071] The polymerizable compound (B) is a compound having an ethylenic double bond, preferably the aforementioned polymerizable group (V), and preferably contains a polymerizable compound (BX) different from the polymerizable compound (B1) (hereinafter, sometimes referred to as other polymerizable compounds (BX)). The proportion of the polymerizable compound (B1) in the polymerizable compound (B) is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, for example, 80% by mass or less, preferably 60% by mass or less, more preferably 40% by mass or less. The proportion of other polymerizable compounds (BX) in the polymerizable compound (B) is, for example, 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, for example, 95% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less.

[0072] As other polymerizable compounds (BX), preferably, polymerizable compounds (BX2) not containing aromatic heterocycles may be mentioned, such as polyfunctional compounds (B2) having a non-cyclic structure, polyfunctional compounds (B3) having hydrocarbon rings, monofunctional compounds (B4), etc. These other polymerizable compounds (BX) may be one kind or a combination of two or more kinds. As other polymerizable compounds, monofunctional compounds (B4) are preferred.

[0073] Examples of the non-cyclic polyfunctional compound (B2) include compounds having two or more (meth)acryloyl groups, and examples of the non-cyclic bifunctional compound include di(meth)acrylates of alkanediols having 1 to 40 carbon atoms in which the methylene group is replaced by -O-, such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol (meth)acrylate, 1,9-nonanediol (meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0074] Examples of the trifunctional or higher-functional compound having a non-cyclic structure include esters of diols having 4 to 40 carbon atoms and which have three or more hydroxyl groups and may have an ether bond and 3 to 6 (meth)acrylic acids, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0075] As the polyfunctional compound (B3) having a hydrocarbon ring, there can be exemplified compounds having two or more (meth)acryloyl groups. As the bifunctional compound having a hydrocarbon ring, there can be cited di(meth)acrylates of cycloalkane diols having about 4 to 8 carbon atoms, such as tricyclodecane dimethanol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and cyclopentane dimethanol di(meth)acrylate; di(meth)acrylates of diols obtained by etherifying the OH group of bisphenols with hydroxyalkylene, such as propoxylated bisphenol A di(meth)acrylate and ethoxylated bisphenol A di(meth)acrylate; and 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene.

[0076] Examples of the trifunctional or higher-functional compound having a hydrocarbon ring include ethoxylated isocyanuric acid tri(meth)acrylate and ε-caprolactone-modified tri-(2-acryloyloxyethyl)isocyanurate.

[0077] Examples of the monofunctional compound (B4) include (meth)acrylate esters of alkanols having 1 to 12 carbon atoms, such as ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; (meth)acrylate esters of alkylene glycol monoethers, such as ethyl diethylene glycol (meth)acrylate; monofunctional compounds having a hydrocarbon ring, such as dicyclopentadiene (meth)acrylate, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and benzyl (meth)acrylate; and monofunctional compounds having a nitrogen atom, such as (meth)acryloylmorpholine and 7-amino-3,7-dimethyloctyl (meth)acrylate.

[0078] In the curable composition, the polymerizable compound (B) is, for example, 80% by mass or less, preferably 70% by mass or less, and more preferably 60% by mass or less. The lower the content of the polymerizable compound (B), the higher the refractive index of the film obtained from the curable composition becomes, and the efficiency of extracting light from the light-emitting layer is improved. The content of the polymerizable compound (B) is, for example, 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more.

[0079] <Polymerization initiator (C)>

[0080] The polymerization initiator (C) is not particularly limited as long as it is a compound that can generate active free radicals, acids, etc. under the action of light or heat to initiate polymerization. Known polymerization initiators can be used, and photopolymerization initiators are preferred. As polymerization initiators that generate active free radicals, for example, O-acyl oxime compounds, alkyl phenone compounds, triazine compounds, acyl phosphine oxide compounds, phosphonate compounds, biimidazole compounds, etc. can be cited. These polymerization initiators can be used alone or in combination of two or more.

[0081] The O-acyl oxime compound is a compound having a partial structure represented by formula (c1).

[0082] [Chemical formula 5]

[0083]

[0084] Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, and N-acetoxy-1-[4-phenylsulfanylphenyl]octane-1-one-2-imine.

[0063] N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolanylmethoxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imide, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imide, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imide, etc. Commercially available products such as Irgacure OXE01, OXE02 (each manufactured by BASF), and N-1919 (manufactured by ADEKA) can be used.

[0085] The alkylphenone compound is a compound having a partial structure represented by formula (c2) or a partial structure represented by formula (c3). In these partial structures, the benzene ring may have a substituent.

[0086] [Chemical formula 6]

[0087]

[0088] Examples of the compound having a partial structure represented by formula (c2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) can be used.

[0089] Examples of the compound having a partial structure represented by formula (c3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-〔4-(2-hydroxyethoxy)phenyl〕propane-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, benzyl dimethyl ketal, and the like.

[0090] 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-methoxyphenyl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine. [2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0091] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can be used.

[0092] Examples of the phosphonate compound include ethyl (2,4,6-trimethylbenzoyl)phenylphosphonate, and commercially available products such as Omnirad TPO-L (manufactured by IGM Resins BV) can be used.

[0093] 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, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, Japanese Patent Application Laid-Open No. 7-10913).

[0094] In addition, 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'-tetrakis (tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, and titanocene compounds, etc. These are preferably used in combination with the polymerization initiator aid (C1) (especially amines) described later.

[0095] The polymerization initiator (C) also includes an acid generator. 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, nitrobenzyl toluenesulfonates, and benzoin toluenesulfonates.

[0096] The polymerization initiator (C) is preferably a polymerization initiator comprising at least one selected from the group consisting of O-acyl oxime compounds, alkyl phenone compounds, triazine compounds, acyl phosphine oxide compounds, phosphonate compounds, and biimidazole compounds, more preferably a polymerization initiator comprising at least one selected from the group consisting of acyl phosphine oxide compounds and phosphonate compounds, and further preferably a phosphonate compound.

[0097] When containing at least one selected from the group consisting of acylphosphine oxide compounds and phosphonate compounds, the total content of acylphosphine oxide compounds and phosphonate compounds in the polymerization initiator (C) is, for example, 50 mass % or more, preferably 70 mass % or more, more preferably 90 mass % or more, and can be 100 mass %.

[0098] The content of the polymerization initiator (C) relative to 100 parts by mass of the polymerizable compound (B) is, for example, 0.1% by mass or more, preferably 1% by mass or more, more preferably 10% by mass or more, for example, 40% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less.

[0099] <Polymerization initiator aid (C1)>

[0100] The polymerization initiator aid (C1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound that is initiated to polymerize by a polymerization initiator. When the polymerization initiator aid (C1) is contained, it is usually used in combination with a polymerization initiator (C).

[0101] Examples of the polymerization initiation aid (C1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0102] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 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. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

[0103] 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.

[0104] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0105] 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.

[0106] When a polymerization initiator aid (C1) is used, its content is, for example, 0.1% by mass or more, preferably 1% by mass or more, more preferably 10% by mass or more, and for example, 40% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less, relative to 100 parts by mass of the polymerizable compound (B).

[0107] The curable composition may contain a resin (D), a solvent (E), and the like as necessary.

[0108] <Resin (D)>

[0109] The resin (D) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (D) include the following resins [K1] to [K6].

[0110] Resin [K1]: A copolymer having a structural unit derived from at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)") and a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)");

[0111] Resin [K2]: a copolymer having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)");

[0112] Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c);

[0113] Resin [K4]: a copolymer having a structural unit in which (b) is added to a structural unit derived from (a), and a structural unit derived from (c);

[0114] Resin [K5]: a copolymer having a structural unit in which (a) is added to a structural unit derived from (b), and a structural unit derived from (c);

[0115] Resin [K6]: A copolymer having a structural unit in which (a) is added to a structural unit derived from (b) and a carboxylic acid anhydride is further added, and a structural unit derived from (c).

[0116] Specific examples of (a) include:

[0117] Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

[0118] 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, etc.;

[0119] Bicyclic unsaturated compounds containing a carboxyl group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[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, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

[0120] Unsaturated dicarboxylic 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;

[0121] Unsaturated mono-(meth)acryloyloxyalkyl) esters of polycarboxylic acids having a valence of 2 or more, such as mono-(2-(meth)acryloyloxyethyl) succinate and mono-(2-(meth)acryloyloxyethyl) phthalate;

[0122] Unsaturated acrylic acid esters containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid, etc.

[0123] Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferred from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an alkaline aqueous solution.

[0124] (b) refers to, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0125] In addition, in this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0126] As (b), for example, there can be mentioned a monomer (b1) having an ethylene oxide group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc.

[0127] As (b1), for example, there can be mentioned a monomer (b1-1) having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)") and a monomer (b1-2) having a structure in which alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

[0128] Examples of (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl o-vinylbenzyl glycidyl ether, α-methyl m-vinylbenzyl glycidyl ether, α-methyl p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl) Styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tri(glycidyloxymethyl)styrene, 2,3,5-tri(glycidyloxymethyl)styrene, 2,3,6-tri(glycidyloxymethyl)styrene, 3,4,5-tri(glycidyloxymethyl)styrene, 2,4,6-tri(glycidyloxymethyl)styrene, and the like.

[0129] Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Co., Ltd.), compounds represented by formula (I) and compounds represented by formula (II), etc.

[0130] [Chemical formula 7]

[0131]

[0132] [In formula (I) and formula (II), R a and R b It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group.

[0133] X a and X b Indicates a single bond, *-R c -、*-R c -O-, *-R c -S- or *-R c -NH-.

[0134] R c It represents an alkanediyl group having 1 to 6 carbon atoms.

[0135] * indicates a bond with O. ]

[0136] Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

[0137] Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl and 4-hydroxybutyl.

[0138] As R a and R b , preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are mentioned, and more preferably, a hydrogen atom and a methyl group are mentioned.

[0139] Examples of the alkane diyl group include a methylene group, an 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.

[0140] As X a and X b Preferred examples include a single bond, a methylene group, a vinyl group, *-CH2-O- and *-CH2CH2-O-, and more preferred examples include a single bond and *-CH2CH2-O- (* represents a bond to O).

[0141] Examples of the compound represented by formula (I) include compounds represented by any one of formula (I-1) to formula (I-15). Among them, preferred are compounds represented by formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15), and more preferred are compounds represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

[0142] [Chemical formula 8]

[0143]

[0144] [Chemical formula 9]

[0145]

[0146] As the compound represented by formula (II), there can be mentioned compounds represented by any one of formula (II-1) to formula (II-15). Among them, preferred are compounds represented by formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15), and more preferred are compounds represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

[0147] [Chemical formula 10]

[0148]

[0149] [Chemical formula 11]

[0150]

[0151] The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination of two or more. When the compound represented by formula (I) and the compound represented by formula (II) are used in combination, their content ratio [compound represented by formula (I): compound represented by formula (II)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

[0152] As (b2), a monomer having an oxetane group and a (meth)acryloyloxy group is more preferred. As (b2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. can be mentioned.

[0153] As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group is more preferred. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0154] As (b), (b1) is preferred from the viewpoint of further improving the reliability of the obtained color filter, such as heat resistance and chemical resistance, and (b1-2) is more preferred from the viewpoint of excellent storage stability of the curable composition.

[0155] As (c), for example, there can be mentioned:

[0156] Methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 ] decane-8-yl ester (in the technical field, it is commonly known as "dicyclopentanyl (meth)acrylate". In addition, it is sometimes referred to as "tricyclodecyl (meth)acrylate".), tricyclo[5.2.1.0 2,6 (Meth)acrylates such as decen-8-yl ester (also known as "dicyclopentenyl (meth)acrylate" as a common name in the art), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

[0157] (Meth)acrylates containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

[0158] Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters;

[0159] 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-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-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene Bicyclic unsaturated compounds such as bicyclo[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, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 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-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene;

[0160] Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide;

[0161] Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

[0162] Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene and the like are preferred from the viewpoint of copolymerization reactivity and heat resistance.

[0163] In the resin [K1], the ratio of the structural units derived from each of the above among all the structural units constituting the resin [K1] is preferably:

[0164] Structural unit derived from (a): 2 to 60 mol%

[0165] Structural unit derived from (b): 40 to 98 mol %

[0166] More preferably:

[0167] Structural unit derived from (a): 10 to 50 mol%

[0168] Structural unit derived from (b): 50 to 90 mol %.

[0169] When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the curable composition, the developability during pattern formation, and the solvent resistance of the obtained developed product tend to be excellent.

[0170] The resin [K1] can be produced, for example, by referring to the method described in the document "Experimental Methods for Polymer Synthesis" (Polymer Synthesis Experimental Methods) (Otsu Takayuki, Chemical Dojin, 1st edition, 1st print, published on March 1, 1972) and the cited documents described in the document.

[0171] Specifically, the following method can be cited: a specified amount of (a) and (b), a polymerization initiator and a solvent are added to a reaction container, for example, oxygen is replaced with nitrogen to form a deoxygenated atmosphere, and heating and heat preservation are performed while stirring. It should be noted that the polymerization initiator and solvent used here are not particularly limited, and substances commonly used in this field can be used. For example, as a polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile)), an organic peroxide (benzoyl peroxide, etc.) can be cited, and as a solvent, as long as each monomer is dissolved, the solvent (E) of the curable composition and the solvent described later can be cited.

[0172] It should be noted that, as for the obtained copolymer, the solution after the reaction can be used directly, the solution after concentration or dilution can be used, and the substance taken out in the form of solid (powder) by a method such as reprecipitation can be used. In particular, by using the solvent (E) contained in the curable composition as the solvent during the polymerization, the solution after the reaction can be directly used for the preparation of the curable composition, thereby simplifying the manufacturing process of the curable composition.

[0173] In the resin [K2], the ratio of the structural units derived from each of the above among all the structural units constituting the resin [K2] is preferably:

[0174] Structural unit derived from (a): 2 to 45 mol%

[0175] Structural unit derived from (b): 2 to 95 mol%

[0176] Structural unit derived from (c): 1 to 65 mol %

[0177] More preferably:

[0178] Structural unit derived from (a): 5 to 40 mol%

[0179] Structural unit derived from (b): 5 to 80 mol%

[0180] Structural unit derived from (c): 5 to 60 mol %.

[0181] When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the curable composition, the developability during pattern formation, and the solvent resistance, heat resistance, and mechanical strength of the obtained developed product tend to be excellent.

[0182] The resin [K2] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0183] In the resin [K3], the ratio of the structural units derived from each of the above among all the structural units constituting the resin [K3] is preferably:

[0184] Structural unit derived from (a): 2 to 60 mol%

[0185] Structural unit derived from (c): 40 to 98 mol %

[0186] More preferably:

[0187] Structural unit derived from (a): 10 to 50 mol%

[0188] Structural unit derived from (c): 50 to 90 mol %.

[0189] The resin [K3] can be produced, for example, in the same manner as described as the method for producing the resin [K1].

[0190] The resin [K4] can be produced by obtaining a copolymer of (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic anhydride contained in (a).

[0191] First, a copolymer of (a) and (c) is produced in the same manner as described as the method for producing resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same ratio as that exemplified in resin [K3].

[0192] Next, the cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the above copolymer.

[0193] After producing the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, (b), a reaction catalyst for carboxylic acid or carboxylic anhydride and cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), and a polymerization inhibitor (e.g., hydroquinone, etc.) are added to the flask, and the mixture is reacted at, for example, 60 to 130° C. for 1 to 10 hours, thereby producing resin [K4].

[0194] The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). By setting it within this range, there is a tendency that the storage stability of the curable composition, the developability when forming a pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained developer become better. Considering the high reactivity of the cyclic ether and the difficulty in leaving unreacted (b), the (b) used in the resin [K4] is preferably (b1), and more preferably (b1-1).

[0195] The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c).

[0196] The reaction conditions such as charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the heat generated by polymerization, etc. It should be noted that the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the heat generated by polymerization, etc., similarly to the polymerization conditions.

[0197] Regarding resin [K5], as a first step, a copolymer of (b) and (c) is obtained in the same manner as in the production method of resin [K1]. As in the above, the obtained copolymer may be used directly as a solution after the reaction, or may be used as a concentrated or diluted solution, or may be used as a solid (powder) obtained by a method such as reprecipitation.

[0198] The ratio of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the above-mentioned copolymer is preferably:

[0199] Structural unit derived from (b): 5 to 95 mol%

[0200] Structural unit derived from (c): 5 to 95 mol %

[0201] More preferably:

[0202] Structural unit derived from (b): 10 to 90 mol%

[0203] Structural unit derived from (c): 10 to 90 mol %.

[0204] Furthermore, under the same conditions as in the method for producing resin [K4], the carboxylic acid or carboxylic anhydride contained in (a) is reacted with the cyclic ether derived from (b) contained in the copolymer of (b) and (c), thereby obtaining resin [K5].

[0205] The amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol relative to 100 mol of (b). From the viewpoint that the cyclic ether has high reactivity and that unreacted (b) is less likely to remain, (b) used in the resin [K5] is preferably (b1), and more preferably (b1-1).

[0206] The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride. The carboxylic acid anhydride is reacted with a hydroxyl group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.

[0207] Examples of the carboxylic anhydride include 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, etc. The amount of the carboxylic anhydride used is preferably 0.5 to 1 mol relative to 1 mol of the amount of (a) used.

[0208] Specific examples of the resin (D) include 3,4-epoxycyclohexylmethyl (meth)acrylate / (meth)acrylic acid copolymers, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl ester / (meth)acrylic acid copolymer resins [K1]; (meth)acrylate glycidyl / (meth)acrylate benzyl / (meth)acrylic acid copolymer, (meth)acrylate glycidyl / styrene / (meth)acrylic acid copolymer, acrylic acid 3,4-epoxy tricyclic [5.2.1.0 2,6] decyl ester / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer and the like resins [K2]; benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer and the like resins [K3]; resins obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, ) benzyl acrylate / (meth)acrylic acid copolymer to which glycidyl (meth)acrylate is added [K4]; a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid, a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate with (meth)acrylic acid, etc. [K5]; a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid, and further reacting the resin with tetrahydrophthalic anhydride, etc. [K6], etc.

[0209] Among them, the resin (D) is preferably the resin [K1] and the resin [K2], and particularly preferably the resin [K2].

[0210] The weight average molecular weight of the resin (D) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, the solubility of the unexposed portion in the developer is good, and the resolution of the pattern is improved.

[0211] The dispersion degree [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (D) is preferably 1.1-6, more preferably 1.2-4.

[0212] The acid value of the resin (D) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and further preferably 70 to 135 mg-KOH / g, based on solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (D), and can be determined, for example, by titration using a potassium hydroxide aqueous solution.

[0213] The solid content of the resin (D) in the curable composition is, for example, 200 parts by mass or less, preferably 100 parts by mass or less, more preferably 50 parts by mass or less, further preferably 30 parts by mass or less, particularly preferably 10 parts by mass or less, and may be 0 parts by mass, relative to 100 parts by mass of the polymerizable compound (B).

[0214] <Solvent (E)>

[0215] The solvent (E) is not particularly limited, and a solvent commonly used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO-), an ether ester solvent (a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- in the molecule and not containing -COO-), an alcohol solvent (a solvent containing OH in the molecule and not containing -O-, -CO- and -COO-), an alcohol ketone solvent (a solvent containing OH and -CO- in the molecule), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, etc. can be mentioned.

[0216] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0217] 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, phenethyl ether, and methyl anisole.

[0218] Examples of the ether ester solvent 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-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 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.

[0219] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0220] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

[0221] Examples of the alcohol ketone solvent include dimers of ketones selected from the above-mentioned ketone solvents, such as diacetone alcohol.

[0222] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

[0223] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0224] Among the above-mentioned solvents, organic solvents having a boiling point of 120° C. to 180° C. at 1 atm are preferred from the viewpoint of operability and drying properties. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, methyl ethyl ketone, butyl acetate, 2-heptanone, diacetone alcohol and N,N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate methyl ethyl ketone and ethyl 3-ethoxypropionate are more preferred.

[0225] When the curable composition contains a solvent (E), the content of the solvent (E) in the curable composition is, for example, 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, particularly preferably 10% by mass or less, and most preferably 5% by mass or less. Even if the curable composition of the present invention does not contain a solvent, it has high fluidity and excellent workability.

[0226] <Surfactant (F)>

[0227] The curable composition may contain a surfactant (F). The surfactant (F) may be used as a leveling agent, and examples thereof include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. These surfactants may have a polymerizable group in the side chain.

[0228] Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule, etc. Examples of the surfactant having a siloxane bond in the molecule include octamethylcyclotetrasiloxane. The silicone-based surfactant may be TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KF994, KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Materials Japan Co., Ltd.), etc.

[0229] Examples of the fluorine-based surfactant include surfactants having a fluorine carbon chain in the molecule. Specifically, examples include FLOURAD (registered trademark) FC430, FLOURAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Co., Ltd.), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), SURFLON (registered trademark) S381, SURFLON S382, SURFLON SC101, SURFLON SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Laboratories, Ltd.), etc.

[0230] Examples of the above-mentioned organosilicon-based surfactants having fluorine atoms include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, and more specifically, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC Corporation).

[0231] When the surfactant (F) is contained, its content relative to the total amount of the curable composition may be, for example, 0.001% by mass to 2% by mass, or 0.001% by mass to 1.5% by mass. Its content is preferably 0.001% by mass to 0.2% by mass, more preferably 0.002% by mass to 0.1% by mass, and further preferably 0.005% by mass to 0.07% by mass.

[0232] <Other ingredients>

[0233] The curable composition of the present invention may contain additives known in the technical field such as a filler, other polymer compounds, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, as required.

[0234] <Characteristics of curable composition>

[0235] The viscosity of the curable composition of the present invention at a temperature of 23° C. is, for example, 200 mPa·s or less, preferably 150 mPa·s or less, more preferably 120 mPa·s or less, and particularly preferably 100 mPa·s or less. In addition, the above-mentioned viscosity is, for example, 1 mPa·s or more. If the viscosity is within the above-mentioned range, when a cured film is formed by an inkjet method, clogging of the ink and flight bending are not likely to occur. The above-mentioned viscosity can be measured, for example, by using an E-type viscometer and optimizing the rotation speed of the rotor (preferably 1 rpm).

[0236] The curable composition of the present invention has excellent transmittance of visible light. Specifically, the average transmittance of the cured film obtained by the following film forming method 1 at a wavelength of 400 to 700 nm is 90% or more per 1.0 μm film thickness, preferably 93% or more, and more preferably 95% or more. In addition, the total transmittance of the cured film obtained by the following film forming method 1 within the range of wavelengths of 400 to 700 nm is preferably 90% or more per 1.0 μm film thickness, more preferably 93% or more, and further preferably 95% or more.

[0237] [Film Forming Method 1]

[0238] The curable composition was applied on a glass substrate so that the average thickness of the cured film was within the range of 1.0±0.2 μm, and an LED lamp was used at 2000 J / m 2 The accumulated light quantity is irradiated with UV of wavelength 385nm.

[0239] When the average thickness of the obtained cured film is 1.0 μm, the transmittance T (film thickness 1.0 μm) is directly set as the transmittance per 1.0 μm film thickness, and when the average thickness of the obtained cured film is x μm (x is a value in the range of 1.0±0.2 and not 1.0), based on A=-log 10 T, convert the transmittance T (film thickness x μm) into absorbance A (film thickness x μm), multiply the reciprocal of the film thickness x (μm) by the absorbance A (film thickness x μm), and thus obtain the absorbance A (film thickness 1.0 μm). Then, based on A=-log 10 The transmittance T (at a film thickness of 1.0 μm) was calculated, and the transmittance T per 1.0 μm of film thickness was obtained from this. Then, the transmittance per 1.0 μm of film thickness was calculated as an average value within a wavelength range of 400 to 700 nm.

[0240] The curable composition of the present invention has a high refractive index. Specifically, the refractive index at a wavelength of 550 nm measured using a spectroscopic ellipsometer on a cured film obtained by the following film forming method 2 is, for example, 1.5 or more, preferably 1.6 or more, more preferably 1.7 or more, for example, 3.0 or less, preferably 2.5 or less, more preferably 2.0 or less.

[0241] [Film Forming Method 2]

[0242] Each of the obtained curable compositions was applied onto a 4-inch Si wafer substrate using a spin coater so that the average film thickness of the cured film was 0.5 μm. An LED lamp was used at 2000 J / m 2 The accumulated light quantity is irradiated with UV of wavelength 385nm.

[0243] <Cured film>

[0244] The curable composition can be treated by a wet method such as spin coating, casting, microgravure coating, gravure coating, rod coating, roller coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing, offset printing, inkjet printing, capillary coating, nozzle coating, etc. to prepare a cured film. In addition, a patterned cured film can also be prepared by photolithography, inkjet printing, etc.

[0245] The thickness of the cured film is generally about 1 nm to 50 μm, preferably 1 μm to 50 μm.

[0246] The cured film can be used as a microlens, a sealing material, or the like, and can be particularly preferably used as a microlens, a sealing material, or the like of a light-emitting element.

[0247] Example

[0248] The present invention is described in more detail below with reference to examples, but the present invention is not limited to the following examples at all and can be implemented with appropriate modifications within the scope consistent with the gist of the foregoing and following texts, all of which are included in the technical scope of the present invention.

[0249] Example 1

[0250] [Manufacturing of Inorganic Microparticle Dispersion]

[0251] Benzyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a polymerizable compound to a zirconium oxide dispersion (zirconium oxide / dispersant / methyl ethyl ketone = 55 / 15 / 30, mass ratio, volume average particle size of zirconium oxide: 10 nm), and methyl ethyl ketone was removed by vacuum distillation to obtain a benzyl acrylate dispersion of zirconium oxide particles (hereinafter referred to as an inorganic fine particle dispersion). The residual amount of methyl ethyl ketone was confirmed by gas chromatography (GC) analysis.

[0252] [Preparation of curable composition]

[0253] The component ratio of the inorganic fine particle dispersion was adjusted so that the mass of zirconium oxide particles was 37 parts by mass, the mass of the dispersant was 9 parts by mass, the mass of benzyl acrylate was 31 parts by mass, and the mass of 9-vinyl carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was 15 parts by mass. 8 parts by mass of ethyl (2,4,6-trimethylbenzoyl)phenylphosphonate (Omnirad TPO-L, manufactured by IGM Resins BV, hereinafter referred to as TPO-L) as a polymerization initiator was added, dissolved, and filtered with a PTFE membrane filter to obtain a curable composition 1.

[0254] Example 2

[0255] A curable composition 2 was obtained in the same manner as in Example 1 except that 6-ethyl dinaphthothiophene acrylate (6EDNTA, manufactured by Sugai Chemical Industries, Ltd.) was used as the polymerizable compound instead of 9-vinylcarbazole.

[0256] Example 3

[0257] By the same method as in Example 1, an inorganic fine particle dispersion was prepared.

[0258] The component ratio of the above-mentioned inorganic fine particle dispersion was adjusted so that the mass of zirconium oxide particles was 37 mass parts, the mass of the dispersant was 9 mass parts, the mass of benzyl acrylate was 31 mass parts, and the mass of 9-vinyl carbazole (produced by Tokyo Chemical Industry Co., Ltd.) was 14 mass parts. 1 mass part of octamethylcyclotetrasiloxane (produced by Tokyo Chemical Industry Co., Ltd.) as a surfactant and 8 mass parts of TPO-L as a polymerization initiator were added. After dissolution, the mixture was filtered with a PTFE membrane filter to obtain a curable composition 3.

[0259] Example 4

[0260] A curable composition 4 was obtained in the same manner as in Example 3 except that 6-ethyl dinaphthothiophene acrylate (6EDNTA, manufactured by Sugai Chemical Industries, Ltd.) was used as the polymerizable compound instead of 9-vinylcarbazole.

[0261] Comparative Example 1

[0262] A comparative curable composition 1 was obtained in the same manner as in Example 1, except that benzyl acrylate was not used as the polymerizable compound, and a mixture of tricyclodecane dimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as A-DCP), 1,10-decanediol diacrylate (A-DOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as A-DOD-N) and isobutyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 9-vinylcarbazole, and octamethylcyclotetrasiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the surfactant, and 5 parts by mass of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IRGACURE (registered trademark) 819, manufactured by BASF, also referred to as IRG819) was used as the polymerization initiator instead of 8 parts by mass of TPO-L.

[0263] Comparative curable composition 1 contained 37 parts by mass of zirconium oxide particles, 9 parts by mass of a dispersant, 24 parts by mass of A-DCP, 14 parts by mass of A-DOD-N, 10 parts by mass of isobutyl methacrylate, 5 parts by mass of IRG819, and 1 part by mass of octamethylcyclotetrasiloxane.

[0264] [Evaluation of curable composition]

[0265] The viscosity of each of the obtained curable compositions at a temperature of 23° C. was measured using an E-type viscometer at a rotor rotation speed of 1 rpm.

[0266] [Production and Evaluation of Cured Films 1, 2]

[0267] Each of the obtained curable compositions was applied onto a 2-inch square glass substrate using a spin coater so that the average thickness of the cured film was 10 μm. Then, an LED lamp was used with a wavelength of 385 nm and a cumulative light intensity of 2000 J / m 2 The cured film was obtained by UV irradiation.

[0268] The following evaluations were performed on the obtained cured films and curable compositions. The evaluation results are shown in Table 1.

[0269] 1. Curing (viscosity)

[0270] The surface of the cured film was touched while wearing protective gloves, and a case where no trace of the protective gloves remained on the cured film was rated as ○, and a case where a trace of the protective gloves remained on the cured film was rated as ×.

[0271] 2. Coating properties

[0272] The thickness of the cured film was measured at two locations, and a value of ○ was given when the difference between the two thicknesses was within 5% of the average value of the two thicknesses, and a value of × was given when the difference was greater than 5%.

[0273] [Production and evaluation of cured film 3]

[0274] 3. Transmittance

[0275] Each of the obtained curable compositions was applied onto a 2-inch square glass substrate using a spin coater so that the average thickness of the cured film was 1.0 μm. Then, an LED lamp was used at a wavelength of 385 nm and a cumulative light intensity of 2000 J / m 2 The transmittance of the cured film at 400 nm to 700 nm was measured using a microspectrophotometer, and the average transmittance was taken as the transmittance of the cured film.

[0276] [Production and evaluation of cured film 4]

[0277] 4. Refractive index

[0278] Each of the obtained curable compositions was applied onto a 4-inch Si wafer substrate using a spin coater so that the average film thickness of the cured film was 0.5 μm. 2 The cured product was irradiated with light having a wavelength of 400 nm to 1600 nm at angles of 60°, 70°, and 75° using a spectroscopic ellipsometer, and the refractive index at a wavelength of 550 nm was determined as the refractive index of the cured film.

[0279] The results are shown in Table 1.

[0280] [Table 1]

[0281]

[0282] a-1: Zirconia nanoparticles

[0283] b-1: Benzyl acrylate

[0284] b-2: 9-vinylcarbazole

[0285] b-3:6EDNTA

[0286] b-4: A-DCP

[0287] b-5: A-DOD-N

[0288] b-6: Isobutyl methacrylate

[0289] c-1: TPO-L

[0290] c-2:IRGACURE819

[0291] e-1: Methyl ethyl ketone

[0292] f-1: Octamethylcyclotetrasiloxane

Claims

1. A curable composition comprising inorganic fine particles (A), a polymerizable compound (B), and a polymerization initiator (C), The polymerizable compound (B) is a compound represented by formula (B1b), [Chemical formula 1] In formula (B1b), X is a nitrogen atom, an oxygen atom, or a sulfur atom; When X is an oxygen atom or a sulfur atom, n is 0; When X is a nitrogen atom, n is 1, R 1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, a 1-methylvinyl group, an allyl group, a methallyl group, an acryloyl group, or a methacryloyl group; R 2 ~R 9 is a hydrogen atom, a vinyl group, a 1-methylvinyl group, an allyl group, a methallyl group, an acryloyl group, a methacryloyl group, a vinyloxy group, a 1-methylvinyloxy group, an allyloxy group, a methallyloxy group, an acryloyloxy group, a methacryloyloxy group, an alkyl group having 1 to 20 carbon atoms, or a substituent group, wherein the substituent group is a halogen atom, a hydroxyl group, -NR a R b , nitro, alkoxy having 1 to 10 carbon atoms, or alkoxycarbonyl having 2 to 10 carbon atoms, wherein R a and R b Each is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; Optionally, R 2 ~R 9 Two adjacent groups in the alkylene group are bonded to each other to form an aromatic hydrocarbon ring, and optionally, a vinyl group, a 1-methylvinyl group, an allyl group, a methallyl group, an acryloyl group, a methacryloyl group, a vinyloxy group, a 1-methylvinyloxy group, an allyloxy group, a methallyloxy group, an acryloyloxy group, a methacryloyloxy group, an alkyl group having 1 to 20 carbon atoms, or a substituent group is bonded to the aromatic hydrocarbon ring, and the substituent group is a halogen atom, a hydroxyl group, -NR a R b , nitro, alkoxy having 1 to 10 carbon atoms, or alkoxycarbonyl having 2 to 10 carbon atoms, wherein R a and R b Each is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; Optionally, the alkyl group having 1 to 20 carbon atoms is bonded with a vinyl group, a 1-methylvinyl group, an acryloyl group, a methacryloyl group, a vinyloxy group, a 1-methylvinyloxy group, an allyloxy group, a methallyloxy group, an acryloyloxy group, a methacryloyloxy group or a substituent group, wherein the substituent group is a halogen atom, a hydroxyl group, -NR a R b , nitro, alkoxy having 1 to 10 carbon atoms, or alkoxycarbonyl having 2 to 10 carbon atoms, wherein R a and R b Each is independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; The compound represented by formula (B1b) has one or two groups selected from the group consisting of vinyl, 1-methylvinyl, allyl, methallyl, acryloyl, methacryloyl, vinyloxy, 1-methylvinyloxy, allyloxy, methallyloxy, acryloyloxy, and methacryloyloxy, The curable composition further contains a polymerizable compound (BX2) not containing an aromatic heterocycle, wherein the polymerizable compound (BX2) not containing an aromatic heterocycle is a monofunctional compound. The inorganic fine particles (A) are zirconium oxide.

2. The curable composition according to claim 1, wherein In the curable composition, the content of the inorganic fine particles (A) is 20% by mass or more.

3. A cured film formed from the curable composition according to claim 1 or 2.

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