Hardening components

Abstract

The objective of the present invention is to improve the curing properties of a curable composition. The curable composition according to one aspect of the present invention contains inorganic fine particles (A), a polymerizable compound (B) and a polymerization initiator (C), wherein the polymerizable compound (B) includes a compound (B1), said compound (B1) having , within the same molecule, at least two groups independently selected from (meth)acryloyl groups (K1) and unsaturated hydrocarbon groups (K2). The mean value of the transmittance at a wavelength of 400 to 700 nm of a film formed from the curable composition is 90% or more for a film thickness of 1.0 μｍ.

Description

[Technical Field]

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

[0002] Organic electroluminescent devices are used in display devices, lighting devices, etc., and studies are being conducted to control the refractive index to increase the light extraction efficiency from the light-emitting layer. Patent Document 1 aims to provide a curable composition having a high refractive index, and discloses, for example, a curable composition containing 45 mass% of zirconia nanoparticles, 25 mass% of tricyclodecane dimethanol dimethacrylate as a ring-structure polyfunctional compound, 14 mass% of 1,9-nonanediol dimethacrylate as an acyclic-structure polyfunctional compound, and 10 mass% of isobutyl methacrylate as a monofunctional compound, together with a polymerization initiator and a surfactant. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-61606 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when a polyfunctional compound with a ring structure and a polyfunctional compound with a non-ring structure are combined, the curable composition may not be cured sufficiently.

[0005] An object of the present invention is to provide a curable composition that has excellent curability. [Means for solving the problem]

[0006] The present invention, which can solve the above problems, has the following configuration. [1] A curable composition containing inorganic fine particles (A), a polymerizable compound (B), and a polymerization initiator (C), the polymerizable compound (B) contains a compound (B1), the compound (B1) has, in the same molecule, at least two groups independently selected from the group consisting of a (meth)acryloyl group (K1) which may have an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms bonded thereto, and an unsaturated hydrocarbon group (K2) which may have an aryl group having 6 to 20 carbon atoms bonded thereto, provided that the case where all of the at least two groups are the same (meth)acryloyl group (K1) is excluded, and the (meth)acryloyl group (K1) and the unsaturated hydrocarbon group (K2) may have a substituent; a film formed from the curable composition under predetermined conditions has an average transmittance of 90% or more at wavelengths of 400 to 700 nm per 1.0 μm of film thickness; The predetermined conditions were as follows: the curable composition was applied to a glass substrate so that the average thickness of the cured film was in the range of 1.0±0.2 μm; and an LED lamp was used to irradiate ultraviolet light with a wavelength of 385 nm at an integrated light intensity of 2000 J / m 2 1. A curable composition comprising irradiating the composition with

[0007] [2] The curable composition according to [1], wherein the content of the inorganic fine particles (A) in the curable composition is 20 mass % or more.

[0008] [3] A cured film formed from the curable composition according to [1] or [2]. [Effects of the Invention]

[0009] According to the present invention, the curable composition can have good curability. DETAILED DESCRIPTION OF THE INVENTION

[0010] One aspect of the present invention is a curable composition containing inorganic fine particles (A), a polymerizable compound (B), and a polymerization initiator (C), characterized in that the polymerizable compound (B) contains specific monomers. Such a curable composition has excellent curability, and a film (specifically, a cured film) obtained from the curable composition has excellent visible light transmittance.

[0011] <Inorganic fine particles (A)> The inorganic fine particles (A) are preferably particles that do not have the ability to convert wavelengths into the visible light region, and are preferably particles having a refractive index of 1.6 or higher. The higher the refractive index of the inorganic fine particles (A), the higher the refractive index of the film obtained from the curable composition, and the more efficient light extraction from the light-emitting layer. The refractive index is preferably 1.8 or higher, and more preferably 2.0 or higher. The refractive index may be, for example, 3.5 or lower, or 3.0 or lower. The refractive index is a value at the D line of sodium.

[0012] The inorganic fine particles (A) include oxides and nitrides, 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), Si3 Examples of inorganic fine particles (A) include silicon nitride (N4; refractive index: 2.0), cerium oxide (CeO2; refractive index: 1.9 to 2.0), zinc oxide (ZnO; refractive index: 1.9), yttrium oxide (Y2O3; refractive index: 1.9), antimony-doped tin oxide (ATO; refractive index: 1.7 to 1.9), antimony oxide (SbO5; refractive index: 1.8), aluminum oxide (Al2O3; refractive index: 1.8), and titanium nitride (TiN; refractive index: 1.6). The inorganic fine particles (A) are preferably oxides of elements in Groups 3 to 5 or 12 to 15 of the periodic table or nitrides of elements in Group 4 of the periodic table, more preferably titanium oxide, zirconium oxide, aluminum oxide, niobium oxide, or silicon nitride, and even more preferably titanium oxide or zirconium oxide. These inorganic fine particles (A) may be used singly or in combination of two or more.

[0013] The volume average particle diameter of the inorganic fine particles (A) is, for example, 100 nm or less, preferably 50 nm or less, more preferably 30 nm or less. The smaller the particle diameter, the higher the visible light transmittance of the film obtained from the curable composition. The lower limit of the volume average particle diameter of the inorganic fine particles (A) is not particularly limited, but is, for example, 0.1 nm or more, preferably 0.5 nm or more, more preferably 1.0 nm or more.

[0014] The content of the inorganic fine particles (A) in the curable composition 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 fine particles (A), the higher the refractive index of the film obtained from the curable composition, and the more improved the light extraction efficiency from the light-emitting layer. The content of the inorganic fine particles (A) is, for example, 80% by mass or less, preferably 70% by mass or less, and more preferably 60% by mass or less.

[0015] The inorganic fine particles (A) may be surface-treated with a coupling agent, such as a silane-based coupling agent, a zirconium-based coupling agent, a titanium-based coupling agent, or a phosphorus-based coupling agent, and these may be used alone or in combination of two or more.

[0016] Examples of silane coupling agents include γ-(meth)acryloyloxypropyldimethylmethoxysilane, γ-(meth)acryloyloxypropylmethyldimethoxysilane, γ-(meth)acryloyloxypropyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyldimethylmethoxysilane, phenylmethyldimethoxysilane, phenyldiethylmethoxysilane, phenylethyldimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane.

[0017] Examples of zirconium-based coupling agents include tetrapropyl zirconate, tetrabutyl zirconate, tetra(triethanolamine) zirconate, tetraisopropyl zirconate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium stearate, zirconium stearate butyrate, monoalkoxyzircoaluminate, trialkoxyzircoaluminate, and tetraalkoxyzircoaluminate.

[0018] Examples of titanium-based coupling agents include isopropyl triisostearoyl titanate, isopropyl tristearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctylphosphate) titanate, and isopropyl titanium triisostearate.

[0019] Examples of phosphorus-based coupling agents include isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate, and acryloyloxyethyl phthaloxyethyl diethyl phosphate.

[0020] The inorganic fine particles (A) may be contained in the curable composition together with a dispersant. As the dispersant, any type of dispersant such as nonionic, anionic, or cationic dispersant can be used, and anionic dispersants are preferred. As the anionic dispersant, phosphate ester dispersants can be preferably used.

[0021] As the dispersant, commercially available products can also 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).

[0022] The amount of dispersant is, for example, 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, per 100 parts by mass of inorganic fine particles (A). The greater the amount of dispersant, the more improved the dispersibility of the inorganic fine particles (A). The amount of dispersant is, for example, 100 parts by mass or less, preferably 60 parts by mass or less, more preferably 40 parts by mass or less, per 100 parts by mass of inorganic fine particles (A). The smaller the amount of dispersant, the more increased the refractive index of the curable composition.

[0023] <Polymerizable compound (B)> The polymerizable compound (B) includes a compound (B1). The compound (B1) has at least two groups independently selected from Group A consisting of a (meth)acryloyl group (K1) optionally bonded to an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and an unsaturated hydrocarbon group (K2) having 2 to 20 carbon atoms optionally bonded to an aryl group having 6 to 20 carbon atoms, in the same molecule. The (meth)acryloyl group (K1) and the unsaturated hydrocarbon group (K2) may have a substituent. However, a case where all of the groups selected from Group A are the same (meth)acryloyl group (K1) is excluded (hereinafter referred to as Requirement 1), and this Requirement 1 applies to all of the following preferred embodiments. There are no limitations other than Requirement 1. For example, when two or more groups are the unsaturated hydrocarbon group (K2), they may be the same or different. Furthermore, when three or more groups are selected from Group A, the compound (B1) may have two or more of the same (meth)acryloyl groups (K1) (referred to as group X) as long as at least one of the groups is different from the group X (the different group may be either the (meth)acryloyl group (K1) or the unsaturated hydrocarbon group (K2)). A curable composition containing such a compound (B1) has excellent curability, and a film obtained from the curable composition has excellent visible light transmittance. It is more preferable to exclude an embodiment in which all of the groups selected from Group A are either an acryloyl group to which no alkyl group having 1 to 20 carbon atoms or no aryl group having 6 to 20 carbon atoms is bonded (hereinafter, sometimes referred to as an acryloyl group in the narrow sense) or a methacryloyl group to which no alkyl group having 1 to 20 carbon atoms or no aryl group having 6 to 20 carbon atoms is bonded (hereinafter, sometimes referred to as a methacryloyl group in the narrow sense) (Preferred Embodiment 1). In another preferred embodiment, at least one of the groups selected from Group A is the unsaturated hydrocarbon group (K2) (Preferred Embodiment 2). Furthermore, in another preferred embodiment, at least one of the groups selected from Group A is the (meth)acryloyl group (K1) and at least one is the unsaturated hydrocarbon group (K2) (Preferred Embodiment 3). These Preferred Embodiments 1, 2, and 3 are also applicable to the following preferred embodiments of Compound (B1).

[0024] The alkyl group having 1 to 20 carbon atoms may be either linear or branched. Specific examples of linear or branched alkyl groups 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.

[0025] Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a xylyl group, a trimethylphenyl group, a naphthyl group, etc. The number of carbon atoms in the aryl group is preferably 6 to 15, more preferably 6 to 12, and even more preferably 6 to 9.

[0026] Examples of the substituent include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; hydroxy groups; a R b (R a and R b are each independently 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 or an ethoxy group; an alkoxycarbonyl group having 2 to 10 carbon atoms such as a methoxycarbonyl group or an ethoxycarbonyl group; etc. The substituent may be directly bonded to the (meth)acryloyl group (K1) or the unsaturated hydrocarbon group (K2), or may be bonded to the alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 20 carbon atoms which is optionally bonded to the (meth)acryloyl group (K1) and the unsaturated hydrocarbon group (K2).

[0027] The (meth)acryloyl group (K1) which may have an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms bonded thereto includes an acryloyl group (K11) which may have an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms bonded thereto, and a methacryloyl group (K12) which may have an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms bonded thereto.

[0028] The unsaturated hydrocarbon group (K2) optionally having an aryl group having 6 to 20 carbon atoms bonded thereto preferably includes a vinyl group (K21) optionally having an aryl group having 6 to 20 carbon atoms and / or an alkyl group having 1 to 18 carbon atoms bonded thereto, a 1-methylvinyl group (K22) optionally having an aryl group having 6 to 20 carbon atoms and / or an alkyl group having 1 to 17 carbon atoms bonded thereto, an allyl group (K23) optionally having an aryl group having 6 to 20 carbon atoms and / or an alkyl group having 1 to 17 carbon atoms bonded thereto, a methallyl group (K24) optionally having an aryl group having 6 to 20 carbon atoms and / or an alkyl group having 1 to 16 carbon atoms bonded thereto, and the like.

[0029] The (meth)acryloyl group (K1) is preferably one that does not have an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms (referred to as a (meth)acryloyl group in the narrow sense), the acryloyl group (K11) is preferably one that does not have an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms (referred to as an acryloyl group in the narrow sense), the methacryloyl group (K12) is preferably one that does not have an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms (referred to as a methacryloyl group in the narrow sense), and the unsaturated hydrocarbon group (K2) is preferably one that does not have an aryl group having 6 to 20 carbon atoms (referred to as an unsaturated hydrocarbon group in the narrow sense). The vinyl group (K21) is preferably one that does not have an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 18 carbon atoms (referred to as a vinyl group in the narrow sense), the 1-methylvinyl group (K22) is preferably one that does not have an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 17 carbon atoms (referred to as a 1-methylvinyl group in the narrow sense), the allyl group (K23) is preferably one that does not have an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 17 carbon atoms (referred to as an allyl group in the narrow sense), and the methallyl group (K24) is preferably one that does not have an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 16 carbon atoms (referred to as a methallyl group in the narrow sense).

[0030] The polymerizable compound (B1) preferably contains, in the same molecule, at least two groups independently selected from Group A' consisting of an acryloyl group (K11), a methacryloyl group (K12), a vinyl group (K21), a 1-methylvinyl group (K22), an allyl group (K23), and a methallyl group (K24). The polymerizable compound (B1) must satisfy the aforementioned condition 1 and may also have Preferred Mode 1, Preferred Mode 2, or Preferred Mode 3 (the same applies to the following preferred embodiments). For example, when at least one of the groups selected from Group A' is a vinyl group (K21), a 1-methylvinyl group (K22), an allyl group (K23), or a methallyl group (K24), the polymerizable compound (B1) satisfies Preferred Mode 1 and Preferred Mode 2. Compound (B1) is also preferably an example corresponding to Preferred Embodiment 3, for example, a compound having at least one group selected from an acryloyl group (K11) and a methacryloyl group (K12) and at least one group selected from a vinyl group (K21), a 1-methylvinyl group (K22), an allyl group (K23), and a methallyl group (K24); more preferably a compound having one group selected from an acryloyl group (K11) and a methacryloyl group (K12) and one group selected from a vinyl group (K21), a 1-methylvinyl group (K22), an allyl group (K23), and a methallyl group (K24); and most preferably a compound having one group selected from an acryloyl group (K11) and a methacryloyl group (K12) and one group selected from a vinyl group (K21) and an allyl group (K23).

[0031] Furthermore, the polymerizable compound (B1) preferably does not have a ring structure.

[0032] The number of groups selected from group A is preferably 4 or less, more preferably 3 or less, and most preferably 2.

[0033] The polymerizable compound (B1) is more preferably a compound represented by formula (1) or formula (2).

[0034] [ka] In the formula, R 1a , R 2a , and R 2b each independently represents a single bond or a methylene group.

[0035] L 11 and L 21 represents an alkanediyl group having 1 to 10 carbon atoms. n1 and n2 represent integers of 0 to 4.

[0036] R 11 ~R 13 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0037] R 14 ~R 16 , and R 21 ~R 26 each independently represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 20 or 6 to 18 carbon atoms.

[0038] R 1a and R 14 ~R 16 The total number of carbon atoms in R is 18 or less. 2a and R 24 ~R 26 The total number of carbon atoms in R is 18 or less. 2b and R 21 ~R 23 The total number of carbon atoms is 18 or less. R 1a , R 2a , R 2b , L 11 , L 21 , R 11 ~R 16 , or R 21 ~R 26 When has a carbon atom, a substituent may be bonded to the carbon atom.

[0039] L 11 and L 21The alkanediyl group having 1 to 10 carbon atoms represented by the formula (I) may be either linear or branched. Specific examples of linear or branched alkanediyl groups include methylene, ethanediyl, n-propanediyl, isopropanediyl, n-butanediyl, isobutanediyl, trimethylmethanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, and decanediyl. The alkanediyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4, and even more preferably 2 to 3.

[0040] R 11 ~R 13 and an alkyl group having 1 to 20 carbon atoms represented by the formula: 14 ~R 16 and R 21 ~R 26 The alkyl group having 1 to 16 carbon atoms represented by the formula (I) may be either linear or branched. Specific examples of linear or branched alkyl groups include methyl, ethyl, propyl, isobutyl, butyl, tert-butyl, hexyl, heptyl, octyl, nonyl, decyl, heptadecyl, and undecyl. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 4 carbon atoms.

[0041] R 11 ~R 13 and an aryl group having 6 to 20 carbon atoms represented by R 14 ~R 16 and R 21 ~R 26 Examples of the aryl group having 6 to 20 or 6 to 18 carbon atoms represented by the formula (I) include a phenyl group, a xylyl group, a trimethylphenyl group, a naphthyl group, etc. The number of carbon atoms in the aryl group is preferably 6 to 15, more preferably 6 to 12, and even more preferably 6 to 9.

[0042] Examples of the substituent include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms; hydroxy groups; a R b(R a and R b are each independently 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 or an ethoxy group; an alkoxycarbonyl group having 2 to 10 carbon atoms such as a methoxycarbonyl group or an ethoxycarbonyl group; and the like.

[0043] n1 is preferably 0 to 3, and more preferably 0 to 2.

[0044] n2 is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 to 1.

[0045] The compound represented by formula (1) is preferably a compound having one group selected from a narrowly defined acryloyl group and a narrowly defined methacryloyl group, and one group selected from a narrowly defined vinyl group, a narrowly defined 1-methylvinyl group, a narrowly defined allyl group, and a narrowly defined methallyl group, and specifically, R 11 , R 12 , R 14 , R 15 is a hydrogen atom, and R 13 and R 16 are each independently a hydrogen atom or a methyl group, and R 1a is a single bond or a methylene group. 11 is preferably an ethylene group, a linear propylene group, or a branched propylene group, and specifically, R 1a , R 11 ~R 16 , n1, and L 11 More preferred are compounds No. 1 to 104, which correspond to the combinations shown in Tables 1 and 2. Compounds No. 1 to 8, 27 to 34, 53 to 60, and 79 to 86 are even more preferred, compounds No. 1 to 8 and 27 to 34 are particularly preferred, and compounds No. 2, 5, 28, and 31 are most preferred.

[0046] [Table 1]

[0047] [Table 2]

[0048] The compound represented by formula (2) is preferably a compound having two groups selected from a vinyl group in the narrow sense, a 1-methylvinyl group in the narrow sense, an allyl group in the narrow sense, and a methallyl group in the narrow sense, and specifically, R 21 , R 22 , R 24 , R 25 is a hydrogen atom, and R 23 and R 26 are each independently a hydrogen atom or a methyl group, and R 2a and R 2b are each independently a single bond or a methylene group. 21 is preferably an ethylene group, a linear propylene group, or a branched propylene group, and specifically, R 21 ~R 26 , R 2a , R 2b , L 21 More preferred are compounds Nos. 201 to 356, where n2 is a combination of any of the compounds shown in Tables 3 to 5. Compounds Nos. 201 to 208, 227 to 234, 253 to 260, 279 to 286, 305 to 312, and 331 to 338 are even more preferred, and compounds Nos. 201 to 208 and 227 to 234 are particularly preferred.

[0049] [Table 3]

[0050] [Table 4]

[0051] [Table 5]

[0052] The polymerizable compound (B) may contain a compound having an ethylenic double bond other than the polymerizable compound (B1) (hereinafter, sometimes referred to as "other polymerizable compound"). The proportion of the polymerizable compound (B1) in the polymerizable compound (B) is, for example, 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more or 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may even be 100% by mass.

[0053] Examples of the other polymerizable compounds include a polyfunctional compound (B2) having a non-cyclic structure, a polyfunctional compound (B3) having a cyclic structure, a monofunctional compound (B4), etc. These other polymerizable compounds may be used alone or in combination of two or more.

[0054] Examples of the polyfunctional compound (B2) having a non-cyclic structure include compounds in which the polymerizable groups are two or more identical (meth)acryloyl groups, and examples of bifunctional compounds having a non-cyclic structure include di(meth)acrylates of alkanediols having 1 to 40 carbon atoms in which a methylene group may be replaced with -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 di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

[0055] Examples of the tri- or higher functional compound having a non-cyclic structure include esters of a diol having 4 to 40 carbon atoms and having three or more hydroxyl groups and optionally having an ether bond with 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.

[0056] Examples of the polyfunctional compound (B3) having a ring structure include compounds in which the polymerizable groups are two or more identical (meth)acryloyl groups. Examples of bifunctional compounds having a ring structure include di(meth)acrylates of cycloalkanediols having about 4 to 8 carbon atoms, such as tricyclodecane dimethanol di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, and cyclopentane dimethanol di(meth)acrylate; di(meth)acrylates of diols obtained by hydroxyalkylene etherification of OH groups of bisphenols, such as propoxylated bisphenol A di(meth)acrylate and ethoxylated bisphenol A di(meth)acrylate; and 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene.

[0057] Examples of the tri- or higher functional compound having a ring structure include ethoxylated isocyanuric acid tri(meth)acrylate and ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate.

[0058] Examples of the monofunctional compound (B4) include (meth)acrylates 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)acrylates of alkylene glycol monoethers, such as ethyl diethylene glycol (meth)acrylate; monofunctional compounds having a ring structure, such as dicyclopentadiene (meth)acrylate, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate; and monofunctional compounds having a nitrogen atom, such as (meth)acryloylmorpholine and 7-amino-3,7-dimethyloctyl (meth)acrylate.

[0059] Preferred other polymerizable compounds include a polyfunctional compound (B2) having a non-cyclic structure, a monofunctional compound (B4), etc. When the polymerizable compound (B) contains the polymerizable compound (B1), the polyfunctional compound (B2) having a non-cyclic structure, and / or the monofunctional compound (B4), the total content of the compound (B1), the polyfunctional compound (B2) having a non-cyclic structure, and the monofunctional compound (B4) in the polymerizable compound (B) is, for example, 40% by mass or more, preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may even be 100% by mass.

[0060] The content of the polymerizable compound (B) in the curable composition 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, and the more improved the light extraction efficiency from the light-emitting layer. 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.

[0061] <Polymerization initiator (C)> The polymerization initiator (C) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization, and known polymerization initiators can be used, with photopolymerization initiators being preferred. Examples of polymerization initiators that generate active radicals include O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, phosphinic acid ester compounds, and biimidazole compounds. These polymerization initiators may be used alone or in combination of two or more.

[0062] The O-acyloxime compound is a compound having a partial structure represented by formula (c1): Hereinafter, * represents a bond.

[0063] [ka] 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 Examples include N-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 (registered trademark) OXE01 and OXE02 (both manufactured by BASF) and N-1919 (manufactured by ADEKA) may also be used.

[0064] The alkylphenone compound is a compound having a partial structure represented by formula (c2) or (c3). In these partial structures, the benzene ring may have a substituent. [ka]

[0065] Examples of compounds having a partial structure represented by formula (c2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, etc. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (all manufactured by BASF) may also be used.

[0066] Examples of compounds having a partial structure represented by formula (c3) 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.

[0067] 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, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

[0068] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.

[0069] Examples of the phosphinate compound include ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, etc. Commercially available products such as Omnirad (registered trademark) TPO-L (manufactured by IGM Resins BV) may also be used.

[0070] 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, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy). 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 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).

[0071] 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 are preferably used in combination with the polymerization initiator aid (C1) described below (especially an amine compound).

[0072] 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 tosylates; and benzoin tosylates.

[0073] The polymerization initiator (C) is preferably a polymerization initiator containing at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, phosphinic acid ester compounds, and biimidazole compounds, and more preferably a polymerization initiator containing at least one selected from the group consisting of acylphosphine oxide compounds and phosphinic acid ester compounds.

[0074] When the polymerization initiator (C) contains at least one selected from the group consisting of an acylphosphine oxide compound and a phosphinic acid ester compound, the total content of the acylphosphine oxide compound and the phosphinic acid ester compound in the polymerization initiator (C) is, for example, 50 mass% or more, preferably 70 mass% or more, more preferably 90 mass% or more, and may be 100 mass%.

[0075] The content of the polymerization initiator (C) is, for example, 0.1 mass% or more, preferably 1 mass% or more, more preferably 10 mass% or more, and for example, 40 mass% or less, preferably 30 mass% or less, more preferably 25 mass% or less, relative to 100 mass parts of the polymerizable compound (B).

[0076] <Polymerization initiator aid (C1)> The polymerization initiation aid (C1) is a compound or sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator. When the curable composition contains the polymerization initiation aid (C1), it is usually used in combination with the polymerization initiator (C).

[0077] Examples of the polymerization initiation aid (C1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0078] Examples of the amine compound 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, 4,4'-bis(ethylmethylamino)benzophenone, etc. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.

[0079] 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.

[0080] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0081] 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.

[0082] When the polymerization initiation aid (C1) is used, the content thereof is, for example, 0.1 mass% or more, preferably 1 mass% or more, more preferably 10 mass% or more, and for example, 40 mass% or less, preferably 30 mass% or less, more preferably 25 mass% or less, relative to 100 mass parts of the polymerizable compound (B).

[0083] The curable composition may contain a resin (D), a solvent (E), and the like, as required. <Resin (D)> 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]. Resin [K1]: a copolymer having structural units derived from at least one member (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and structural units derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure and an ethylenically unsaturated bond having 2 to 4 carbon atoms; Resin [K2]: a copolymer having structural units derived from (a), structural units derived from (b), and structural units derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter, sometimes referred to as "(c)"); Resin [K3]: a copolymer having structural units derived from (a) and structural units derived from (c); Resin [K4]: a copolymer having a structural unit derived from (a) to which (b) is added, and a structural unit derived from (c); Resin [K5]: a copolymer having a structural unit derived from (b) to which (a) is added, and a structural unit derived from (c); Resin [K6]: A copolymer having a structural unit derived from (c), and a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride.

[0084] Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic 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, and 1,4-cyclohexenedicarboxylic acid; bicyclounsaturated compounds containing a carboxy 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; 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, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene 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; Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

[0085] Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred from the viewpoint of copolymerization reactivity and solubility of the resulting resin in an alkaline aqueous solution.

[0086] (b) refers to, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, 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.

[0087] In this specification, "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

[0088] Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)").

[0089] Examples of (b1) include a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon has been epoxidized, and a monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon has been epoxidized.

[0090] Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (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(glycidyl Examples of such styrene include 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, and 2,4,6-tris(glycidyloxymethyl)styrene.

[0091] Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., CELLOXIDE (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., CYCLOMER (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., CYCLOMER (registered trademark) M100; manufactured by Daicel Corporation), compounds represented by formula (I), and compounds represented by formula (II).

[0092] [ka]

[0093] In formula (I) and formula (II), R a and R b 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 with a hydroxy group.

[0094] X a and X b is a single bond, *-R c -, *-R c -O-, *-R c -S- or *-R c represents -NH-.

[0095] R c represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.

[0096] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

[0097] Examples of alkyl groups in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.

[0098] R a and R b Preferred examples of the alkyl group include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferred examples include a hydrogen atom and a methyl group.

[0099] Examples of the alkanediyl 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.

[0100] X a and X bPreferred examples of the group include a single bond, a methylene group, an ethylene group, *-CH2-O-, and *-CH2CH2-O-, and more preferred examples include a single bond and *-CH2CH2-O- (* represents a bond to O).

[0101] Examples of the compound represented by formula (I) include compounds represented by any of formulas (I-1) to (I-15). Among them, compounds represented by formula (I-1), (I-3), (I-5), (I-7), (I-9) or (I-11) to (I-15) are preferred, and compounds represented by formula (I-1), (I-7), (I-9) or (I-15) are more preferred.

[0102] [ka]

[0103] [ka]

[0104] Examples of the compound represented by formula (II) include compounds represented by any one of formulas (II-1) to (II-15). Among them, compounds represented by formula (II-1), (II-3), (II-5), (II-7), (II-9), or (II-11) to (II-15) are preferred, and compounds represented by formula (II-1), (II-7), (II-9), or (II-15) are more preferred.

[0105] [ka]

[0106] [ka]

[0107] 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, the content ratio thereof [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.

[0108] As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferred. Examples of (b2) include 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-acryloyloxyethyloxetane, and the like.

[0109] As (b3), a monomer having a tetrahydrofuryl 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.

[0110] (b) is preferably (b1) in that it can further increase the reliability of the heat resistance, chemical resistance, etc. of the film obtained from the curable composition. Furthermore, (b1-2) is more preferred in that it provides excellent storage stability of the curable composition.

[0111] Examples of (c) include 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 ]decan-8-yl(meth)acrylate (commonly known in the art as "dicyclopentanyl(meth)acrylate" and sometimes as "tricyclodecyl(meth)acrylate"), tricyclo[5.2.1.0 2,6 (meth)acrylic acid esters such as ]decen-8-yl (meth)acrylate (commonly known as "dicyclopentenyl (meth)acrylate" in the technical field), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; 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 Bicyclo[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-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, 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 bicyclounsaturated compounds such as 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; 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; Examples include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

[0112] Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, and the like are preferred from the viewpoints of copolymerization reactivity and heat resistance.

[0113] In the resin [K1], the ratio of each structural unit to the total number of moles of all structural units constituting the resin [K1] is: Structural units derived from (a): 2 to 60 mol% Structural units derived from (b): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol% Structural units derived from (b): 50 to 90 mol% It is more preferable that:

[0114] When the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the curable composition, the developability when forming a pattern, and the solvent resistance of the resulting developed product tend to be excellent.

[0115] Resin [K1] can be produced, for example, by referring to the method described in the document "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 therein.

[0116] Specifically, a method can be exemplified in which predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and the atmosphere is deoxygenated, for example by replacing oxygen with nitrogen, followed by heating and keeping the temperature while stirring. The polymerization initiator, solvent, and the like used here are not particularly limited, and those commonly used in the relevant field can be used. For example, polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). Solvents that dissolve the respective monomers can be used, and examples of the solvent (E) for the curable composition include the solvents described below.

[0117] The resulting copolymer may be used as a solution after the reaction as is, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent (E) contained in the curable composition as a solvent during the polymerization, the solution after the reaction can be used as is for preparing the curable composition, thereby simplifying the production process of the curable composition.

[0118] In the resin [K2], the ratio of each structural unit to the total number of moles of all structural units constituting the resin [K2] is: Structural units derived from (a): 2 to 45 mol% Structural units derived from (b): 2 to 95 mol% Structural units derived from (c): 1 to 65 mol% It is preferred that Structural units derived from (a): 5 to 40 mol% Structural units derived from (b): 5 to 80 mol% Structural units derived from (c): 5 to 60 mol% It is more preferable that:

[0119] When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the curable composition, the developability when forming a pattern, and the solvent resistance, heat resistance, and mechanical strength of the resulting developed product tend to be excellent.

[0120] Resin [K2] can be produced, for example, in the same manner as described above for producing resin [K1].

[0121] In the resin [K3], the ratio of each structural unit to the total number of moles of all structural units constituting the resin [K3] is as follows: Structural units derived from (a): 2 to 60 mol% Structural units derived from (c): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol% Structural units derived from (c): 50 to 90 mol% It is more preferable that:

[0122] Resin [K3] can be produced, for example, in the same manner as described above for producing resin [K1].

[0123] Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and then adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic acid anhydride contained in (a).

[0124] First, a copolymer of (a) and (c) is produced in the same manner as described for the production of resin [K1]. In this case, the ratio of each structural unit is preferably the same as that described for resin [K3].

[0125] Next, a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms contained in (b).

[0126] Specifically, following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and (b), a reaction catalyst for the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc. are placed in the flask, and the reaction is carried out, for example, at 60 to 130°C for 1 to 10 hours, thereby producing the resin [K4].

[0127] The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By using (b) in this range, 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 resulting developed product tend to be good. Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) used in resin [K4], and (b1-1) is more preferred.

[0128] The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total of (a), (b), and (c).The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total of (a), (b), and (c).

[0129] The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted taking into consideration the production equipment, the amount of heat generated by polymerization, and the like.

[0130] In the production of resin [K5], in the first step, a copolymer of (b) and (c) is obtained in the same manner as in the production method of resin [K1] described above. As in the above, the obtained copolymer may be used as a solution after the reaction as is, a concentrated or diluted solution, or a solid (powder) obtained by a method such as reprecipitation. The ratio of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer is: Structural units derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:

[0131] Furthermore, under the same conditions as in the production method of resin [K4], resin [K5] can be obtained by reacting the cyclic ether derived from (b) contained in the copolymer of (b) and (c) with the carboxylic acid or carboxylic anhydride contained in (a).

[0132] The amount of (a) used to react with the copolymer is preferably 5 to 80 moles per 100 moles of (b). Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) used in resin [K5], and (b1-1) is more preferred.

[0133] Resin [K6] is a resin obtained by further reacting resin [K5] with a carboxylic acid anhydride. Specifically, the hydroxyl group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride is reacted with the carboxylic acid anhydride.

[0134] Examples of the carboxylic acid 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 acid anhydride used is preferably 0.5 to 1 mole per mole of the amount of (a) used.

[0135] Specific examples of the resin (D) include 3,4-epoxycyclohexylmethyl (meth)acrylate / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6] Decyl acrylate / (meth)acrylic acid copolymer and other resins [K1]; glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer, etc. [K2]; benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer, etc. [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, tricyclodecyl (meth)acrylate / Examples of the resin include [K4] a resin obtained by adding glycidyl (meth)acrylate to a benzyl (meth)acrylate / (meth)acrylic acid copolymer; [K5] a resin obtained by reacting a tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymer with (meth)acrylic acid; and [K6] a resin obtained by reacting a tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymer with (meth)acrylic acid and then reacting tetrahydrophthalic anhydride with the resulting resin.

[0136] Among these, resin (D) is preferably resin [K1] or resin [K2], and resin [K2] is particularly preferred.

[0137] The polystyrene-equivalent weight average molecular weight of the resin (D) 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 film obtained from the curable composition is improved, the residual film rate is high, and the solubility of the unexposed areas in the developer is good, which tends to improve the pattern resolution.

[0138] The polydispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (D) is preferably 1.1-6, more preferably 1.2-4.

[0139] The acid value of the resin (D) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and even more preferably 70 to 135 mg-KOH / g, calculated as solid content. 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 with an aqueous potassium hydroxide solution.

[0140] 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, even more 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).

[0141] <Solvent (E)> The solvent (E) is not particularly limited, and a solvent commonly used in the art can be used. Examples thereof include 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-), alcohol ketone solvents (solvents containing OH and -CO- in the molecule), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

[0142] 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.

[0143] 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.

[0144] 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-methylpropionate, methyl 2-ethoxy ... Examples of the alkyl acrylate copolymer 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.

[0145] Examples of ketone solvents 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.

[0146] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0147] Examples of the alcohol ketone solvent include a dimer of a ketone selected from the above-mentioned ketone solvents, such as diacetone alcohol.

[0148] Aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, and the like.

[0149] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0150] Among the above solvents, organic solvents having a boiling point at 1 atm of 120° C. or higher and 180° C. or lower are preferred from the viewpoints of workability and drying properties. Preferred solvents include 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, and more preferred are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, methyl ethyl ketone, and ethyl 3-ethoxypropionate.

[0151] 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, even more preferably 15% by mass or less, particularly preferably 10% by mass or less, and most preferably 5% by mass or less. The curable composition according to the above aspect of the present invention has high fluidity and excellent workability even without containing a solvent.

[0152] <Surfactant (F)> The curable composition may contain a surfactant (F). The surfactant (F) can be used as a leveling agent, and examples thereof include silicone surfactants, fluorine surfactants, and silicone surfactants containing fluorine atoms. These surfactants may have a polymerizable group in the side chain.

[0153] Examples of silicone surfactants include surfactants having a siloxane bond in the molecule, such as octamethylcyclotetrasiloxane. Commercially available products such as Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade names: manufactured by Dow Corning Toray Co., Ltd.), KF994, KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan, LLC) may also be used.

[0154] Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule, such as Fluorad (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Research Institute, Ltd.).

[0155] Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, such as Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0156] When the curable composition contains a surfactant (F), the content thereof is preferably 0.001 mass % or more and 0.2 mass % or less, more preferably 0.002 mass % or more and 0.1 mass % or less, and even more preferably 0.005 mass % or more and 0.07 mass % or less, relative to the total amount of the curable composition.

[0157] <Other ingredients> The curable composition according to the above aspect of the present invention may contain additives known in the technical field, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, as necessary.

[0158] <Curable composition characteristics> The viscosity of the curable composition according to the above aspect of the present invention at a temperature of 23°C is, for example, 50 mPa·s or less, preferably 45 mPa·s or less, and more preferably 40 mPa·s or less. The viscosity is, for example, 1 mPa·s or more. When the viscosity is within this range, clogging or deflection of the ink is less likely to occur when forming a cured film using an inkjet method. The viscosity can be measured, for example, using an E-type viscometer and optimizing the rotor rotation speed (preferably 1 rpm).

[0159] The curable composition according to the above aspect of the present invention has excellent transmittance for visible light. Specifically, the average transmittance for wavelengths of 400 to 700 nm of the cured film obtained by the following film-forming method 1 is 90% or more, preferably 93% or more, and more preferably 95% or more per 1.0 μm of film thickness. Furthermore, the average transmittance for all wavelengths in the range of 400 to 700 nm of the cured film obtained by the following film-forming method 1 is preferably 90% or more, more preferably 93% or more, and even more preferably 95% or more per 1.0 μm of film thickness. [Film forming method 1] The curable composition was applied to a glass substrate so that the average thickness of the cured film was within the range of 1.0±0.2 μm, and ultraviolet (UV) rays with a wavelength of 385 nm were irradiated using an LED lamp at an integrated light intensity of 2000 J / m 2 Irradiate with.

[0160] When the average thickness of the obtained cured film is 1.0 μm, the transmittance T (when the film thickness is 1.0 μm) is treated as the transmittance per 1.0 μm film thickness. On the other hand, when the average thickness of the obtained cured film is x μm (x is a value within the range of 1.0±0.2 and not 1.0), the transmittance T' (when the film thickness is x μm) is first calculated by the following equation: A'=-log 10 Based on T', convert to absorbance A' (when film thickness is x μm), and multiply this absorbance A' (when film thickness is x μm) by the reciprocal of film thickness x (μm) to obtain absorbance A (when film thickness is 1.0 μm), and then A = -log 10 The transmittance T per 1.0 μm film thickness is determined by calculating the transmittance T (when the film thickness is 1.0 μm) based on T. Then, the average value of the transmittance per 1.0 μm film thickness at wavelengths of 400 to 700 nm is calculated.

[0161] The curable composition according to the above aspect of the present invention has a high refractive index. Specifically, the refractive index at a wavelength of 550 nm of a cured film obtained by the following Film Forming Method 2, as measured using a spectroscopic ellipsometer, is for example 1.5 or more, preferably 1.6 or more, more preferably 1.7 or more, and for example 3.0 or less, preferably 2.5 or less, more preferably 2.0 or less. [Film formation method 2] The curable composition is applied to a 4-inch Si wafer substrate using a spin coater so that the average thickness of the cured film is 0.5 μm. An LED lamp is used to apply UV light with a wavelength of 385 nm at an integrated light intensity of 2000 J / m. 2 Irradiate with.

[0162] <Cured film> A cured film can be produced by treating the curable composition by a wet method such as spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing, offset printing, inkjet printing, capillary coating, nozzle coating, etc. Alternatively, a patterned cured film may be produced by using a photolithography method, inkjet printing, etc.

[0163] The thickness of the cured film is usually about 1 nm to 50 μm, and preferably 1 μm to 50 μm.

[0164] The cured film can be used as a microlens, a sealant, etc., and is particularly preferably used as a microlens, a sealant, etc. for a light-emitting element. [Example]

[0165] 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 it is possible to carry out the invention by making appropriate modifications within the scope of the above-mentioned or below-mentioned purpose, and all such modifications are included in the technical scope of the present invention.

[0166] Example 1 [Production of inorganic particle dispersion] 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), 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA, manufactured by Nippon Shokubai Co., Ltd., hereafter referred to as VEEA) was added as a polymerizable compound, and the methyl ethyl ketone was removed by distillation under reduced pressure to obtain a VEEA dispersion of zirconium oxide particles (zirconia nanoparticles) (hereafter referred to as inorganic fine particle dispersion). The amount of remaining methyl ethyl ketone was confirmed by gas chromatography (GC) analysis. [Preparation of Curable Composition] The inorganic fine particle dispersion was prepared by adjusting the component ratios so that the mass of zirconium oxide particles was 37 parts by mass, the mass of dispersant was 9 parts by mass, and the mass of VEEA was 46 parts by mass. Furthermore, 8 parts by mass of ethylphenyl(2,4,6-trimethylbenzoyl)phosphinate (Omnirad (registered trademark) TPO-L, manufactured by IGM Resins BV, hereinafter referred to as TPO-L) was blended and dissolved as a polymerization initiator, and the mixture was filtered through a polytetrafluoroethylene (PTFE) membrane filter to obtain curable composition 1.

[0167] Example 2 Curable composition 2 was obtained in the same manner as in Example 1, except that allyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of VEEA as the polymerizable compound.

[0168] Example 3 Curable composition 3 was obtained in the same manner as in Example 2, except that 3 parts by mass of methyl ethyl ketone was left as the solvent in the curable composition, and the mass of allyl methacrylate was 43 parts by mass.

[0169] Comparative Example 1 Comparative curable composition 1 was obtained in the same manner as in Example 1, except that 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 VEEA as the polymerizable compound, octamethylcyclotetrasiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.) was further used as the surfactant, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure (registered trademark) 819, manufactured by BASF, hereinafter referred to as IRG819) was used as the polymerization initiator instead of TPO-L.

[0170] 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.

[0171] Examples 4 to 7 Curable compositions 4 to 7 were obtained in the same manner as in Example 1, except that the amount of zirconium oxide particles, the type and amount of polymerizable compound, and the amount of surfactant were changed (or maintained) as shown in Table 6.

[0172] [Evaluation of Curable Composition] The viscosity of each of the obtained curable compositions at a temperature of 23°C was measured using an E-type viscometer with the rotor rotation speed set to 1 rpm.

[0173] [Production and evaluation of cured films 1, 2] Each of the obtained curable compositions was applied to 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 to apply the cured film with a wavelength of 385 nm and an integrated light intensity of 2000 J / m 2 The coating was then irradiated with UV light at 1000 kJ / min to obtain a cured film.

[0174] The obtained cured films and curable compositions were evaluated as follows. The evaluation results are shown in Table 6. 1. Hardening (tackiness) The surface of the cured film was touched while wearing protective gloves, and the case where the protective gloves left no mark on the cured film was evaluated as ◯, and the case where the protective gloves left a mark on the cured film was evaluated as x. 2.Applicability The thickness of the cured film was measured at two points, and if the difference between the two film thicknesses was within 5% of the average value of the two film thicknesses, it was evaluated as ◯, and if it was more than 5%, it was evaluated as x.

[0175] [Production of cured films and their evaluation 3] 3.Transmittance Each of the obtained curable compositions was applied to 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 to apply the cured film with a wavelength of 385 nm and an integrated light intensity of 2000 J / m 2 The transmittance of the cured film in the range of 400 nm to 700 nm was measured using a microspectrophotometer, and the average transmittance was evaluated as the transmittance of the cured film.

[0176] [Production and evaluation of cured films 4] 4. Refractive Index The curable composition was applied onto a 4-inch Si wafer substrate using a spin coater so that the average thickness of the cured film was 0.5 μm. Then, an LED lamp was used to apply the curable composition, emitting light at a wavelength of 385 nm and an integrated light intensity of 2000 J / m 2Using a spectroscopic ellipsometer, the cured film was irradiated with light in the wavelength range of 400 nm to 1600 nm at angles of 60°, 70°, and 75° to determine the refractive index at a wavelength of 550 nm, which was then evaluated as the refractive index of the cured film.

[0177] The results are shown in Table 6.

[0178] [Table 6]

Claims

1. A curable composition containing inorganic fine particles (A), a polymerizable compound (B), and a polymerization initiator (C), The polymerizable compound (B) contains a compound represented by formula (1): 【Chemistry 1】 [In formula (1), R １ａ represents a single bond or a methylene group, L １１ represents an alkanediyl group having 1 to 10 carbon atoms, n1 represents an integer of 0 to 4; R １１ ~R １３ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R １４ ~R １６ each independently represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 18 carbon atoms. the content of the polymerizable compound (B) in the curable composition is 40% by mass or more and 80% by mass or less, the polymerization initiator (C) is a phosphinic acid ester compound, a film formed from the curable composition under predetermined conditions has an average transmittance of 90% or more at wavelengths of 400 to 700 nm per 1.0 μm of film thickness; The predetermined conditions were as follows: the curable composition was applied to a glass substrate so that the average thickness of the cured film was in the range of 1.0±0.2 μm; and ultraviolet light having a wavelength of 385 nm was applied using an LED lamp with an integrated light intensity of 2000 J / m ２ 1. A curable composition comprising irradiating the composition with

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

Images