Curable composition and cured film

Abstract

Provided is a curable composition having excellent storage stability. The present invention relates to a curable composition containing a polymerizable compound having an aromatic heterocyclic ring, inorganic fine particles, a compound represented by formula (I), and a polymerization initiator. In formula (I), RN1, RN2, and RN3 represent a hydrogen atom, a saturated hydrocarbon group having 1-20 carbon atoms, or the like.

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, and other applications. Research is underway to control the refractive index to improve the efficiency of light extraction from the light-emitting layer. Patent Document 1 aims to provide a curable composition with a high refractive index. For example, it discloses a curable composition comprising 45% by mass of zirconium oxide nanoparticles, 25% by mass of tricyclodecane dimethanol dimethacrylate as a cyclic multifunctional compound, 14% by mass of 1,9-nonanediol dimethacrylate as an acyclic multifunctional compound, 10% by mass of isobutyl methacrylate as a monofunctional compound, a polymerization initiator, and a surfactant.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2017-61606 Summary of the Invention

[0006] However, it is desired that the curable composition have excellent storage stability. Therefore, an object of the present invention is to provide a curable composition having excellent storage stability and a cured film using the same.

[0007] [1] A polymerizable compound having an aromatic heterocycle, inorganic fine particles, and a compound represented by formula (I)

[0008]

[0009] [In formula (I), R N1 、R N2 and R N3 Each of them independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a group represented by the following formula (II), R N1 、R N2 and R N3 At least one of them is a saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by the following formula (II), R N1 、R N2 and R N3 Two of them can bond to each other to form a ring.]

[0010]

[0011] [In formula (II), Q represents a group that forms an aromatic hydrocarbon ring having 6 to 20 carbon atoms together with 3 carbon atoms.]

[0012] [2] The curable composition according to [1], wherein the content of the compound represented by formula (I) is 0.1 mol% or more based on the total amount of the polymerizable compound having an aromatic heterocycle.

[0013] [3] The curable composition according to [1] or [2], wherein the group represented by formula (II) is a phenyl group.

[0014] [4] The curable composition according to any one of [1] to [3], wherein the saturated hydrocarbon group is an alkyl group.

[0015] [5] A cured film formed from the curable composition according to any one of [1] to [4].

[0016] According to the present invention, there can be provided a curable composition having excellent storage stability and a cured film using the same. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 This is a graph showing the relationship between Strain [nm] (indentation depth) and Load [nm] (test load) of the cured films formed from the curable compositions of Examples 7 to 10. DETAILED DESCRIPTION

[0018] Several embodiments of the present invention are described in detail below, but the present invention is not limited to the following embodiments.

[0019] In this specification, a numerical range expressed using "to" indicates a range including the numerical values ​​described before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper limit or lower limit described in one numerical range can be replaced by the upper limit or lower limit of another numerical range described in stages. In addition, in the numerical ranges described in this specification, the upper limit or lower limit of the numerical range can be replaced by the value shown in the Examples.

[0020] In this specification, (meth)acrylate refers to acrylate or its corresponding methacrylate. The same applies to other similar expressions such as (meth)acrylic acid, (meth)acryloyl, etc.

[0021] In this specification, unless otherwise specified, the materials listed below may be used alone or in combination of two or more within the specified range. If there are multiple substances belonging to each component, the content of each component refers to the total amount of the multiple substances unless otherwise specified.

[0022] (Curable composition)

[0023] The curable composition of the present embodiment contains a polymerizable compound having an aromatic heterocyclic ring, inorganic fine particles, a compound represented by formula (I), and a polymerization initiator.

[0024]

[0025] [In formula (I), R N1 、R N2 and R N3 Each of them independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a group represented by the following formula (II), R N1 、R N2 and R N3 At least one of them is a saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by the following formula (II), R N1 、R N2 and R N3 Two of them can bond to each other to form a ring.]

[0026]

[0027] [In formula (II), Q represents a group that forms an aromatic hydrocarbon ring having 6 to 20 carbon atoms together with 3 carbon atoms.]

[0028] Such a curable composition is excellent in storage stability.

[0029] Hereinafter, each component of the curable composition will be described.

[0030] <Polymerizable compounds having aromatic heterocycles>

[0031] The curable composition of the present embodiment contains a polymerizable compound having an aromatic heterocycle. The polymerizable compound having an aromatic heterocycle may contain a polymerizable group and an aromatic heterocycle.

[0032] Examples of the polymerizable group include 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.

[0033] Examples of the aromatic heterocycle include nitrogen-containing aromatic heterocycles, sulfur-containing aromatic heterocycles, and oxygen-containing aromatic heterocycles.

[0034] Specific examples of the aromatic heterocycle include a pyrrole ring which may be fused with another ring, a thiophene ring which may be fused with another ring, and a furan ring which may be fused with another ring.

[0035] A substituent or an alkyl group having 1 to 20 carbon atoms may be bonded to the pyrrole ring which may be fused to another ring, the thiophene ring which may be fused to another ring, and the furan ring which may be fused to another ring, and a substituent may be bonded to the alkyl group having 1 to 20 carbon atoms.

[0036] Examples of the pyrrole ring that may be fused with another ring include a pyrrole ring, an indole ring, an isoindole ring, a carbazole ring, a naphthopyrrole ring, and a dinaphthopyrrole ring. Examples of the thiophene ring that may be fused with another ring include a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a naphthothiophene ring, and a dinaphthothiophene ring. Examples of the furan ring that may be fused with another ring include a furan ring, a benzofuran ring, a dibenzofuran ring, a naphthofuran ring, and a dinaphthofuran ring.

[0037] The alkyl group having 1 to 20 carbon atoms may be either linear or branched. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, isobutyl, butyl, tert-butyl, hexyl, heptyl, octyl, nonyl, decyl, heptadecyl, and undecyl. The number of carbon atoms in these alkyl groups may be, for example, 1 to 12, 1 to 8, or 1 to 4.

[0038] 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 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; and an alkoxycarbonyl group having 2 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group.

[0039] The polymerizable compound having an aromatic heterocyclic ring may be, for example, a compound represented by the following formula (B1b) (hereinafter, sometimes referred to as compound (B1b)).

[0040]

[0041] [Wherein, X is a nitrogen atom, an oxygen atom or a sulfur atom.

[0042] When X is an oxygen atom or a sulfur atom, n is 0.

[0043] 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.

[0044] R 2 ~R 9is a hydrogen atom, vinyl, 1-methylvinyl, allyl, methallyl, acryloyl, methacryloyl, vinyloxy, 1-methylvinyloxy, allyloxy, methallyloxy, acryloyloxy, methacryloyloxy, an alkyl group having 1 to 20 carbon atoms, or a substituent, and R 2 ~R 9 Adjacent two of the groups may be bonded to each other to form an aromatic hydrocarbon ring, and a vinyl group, 1-methylvinyl group, allyl group, methallyl group, acryloyl group, methacryloyl group, vinyloxy group, 1-methylvinyloxy group, allyloxy group, methallyloxy group, acryloyloxy group, methacryloyloxy group, alkyl group having 1 to 20 carbon atoms, or a substituent may be bonded to the aromatic hydrocarbon ring.

[0045] 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.

[0046] The above substituents are halogen atoms, hydroxyl groups, -NR a R b (Ra and Rb 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, or an alkoxycarbonyl group having 2 to 10 carbon atoms.

[0047] The compound represented by formula (B1b) has 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 (hereinafter sometimes referred to as "polymerizable group (V)").

[0048] X is preferably a nitrogen atom or a sulfur atom.

[0049] Compound (B1b) may be, for example, R 2 ~R 9 The embodiment (embodiment a) in which all R are hydrogen atoms or polymerizable groups (V), or 2 ~R 9 Two adjacent ones of the rings are bonded to form an aromatic hydrocarbon ring and R 2 ~R 9 An embodiment in which the group not constituting the aromatic hydrocarbon ring is a hydrogen atom or a polymerizable group (V) (embodiment b).

[0050] 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.

[0051] Examples of the alkyl group having 1 to 20 carbon atoms constituting compound (B1b) include the same groups as those constituting the polymerizable compound having an aromatic heterocycle. Examples of the substituent group constituting compound (B1b) include the same groups as those constituting the polymerizable compound having an aromatic heterocycle.

[0052] Compound (B1b) has one or two groups selected from vinyl, allyl, allyloxy, acryloyl, methacryloyl, acryloyloxy and methacryloyloxy, and preferably has one group selected from vinyl, allyl, allyloxy, acryloyl, acryloyloxy and methacryloyloxy.

[0053] When X is a nitrogen atom, R 1 Preferably, it is 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 or a methacryloyloxy group.

[0054] When X is an oxygen atom or a sulfur atom, R 2 ~R 9 One or two of them are each independently preferably 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 or a methacryloyloxy group.

[0055] Specific examples of the polymerizable compound having an aromatic heterocycle include compounds represented by Formula (B1c-1), Formula (B1c-2), Formula (B1c-3), Formula (B1c-4), Formula (B1d-1), Formula (B1d-2), Formula (B1d-3), Formula (B1d-4), Formula (B1d-5), Formula (B1d-6), and Formula (B1d-7). Among them, the compound represented by Formula (B1c-1) or Formula (B1d-5) is preferred.

[0056]

[0057] The polymerizable compound having an aromatic heterocyclic ring can be used alone or in combination of two or more.

[0058] In the curable composition, from the viewpoint of the high refractive index of the cured product obtained, based on the total mass of the curable composition, the content of the polymerizable compound with an aromatic heterocycle can be, for example, 5% by mass or more, 10% by mass or more, or 15% by mass or more. From the viewpoint of the uniformity (solubility, cohesion) of the curable composition, based on the total mass of the curable composition, the content of the polymerizable compound with an aromatic heterocycle can be, for example, 50% by mass or less, 40% by mass or less, or 30% by mass or less. From these viewpoints, based on the total mass of the curable composition, the content of the polymerizable compound with an aromatic heterocycle can be, for example, 5 to 50% by mass, 10 to 40% by mass, or 15 to 30% by mass or less.

[0059] <Other polymerizable compounds>

[0060] The curable composition of this embodiment may further contain a polymerizable compound other than the polymerizable compound having an aromatic heterocycle. The polymerizable compound may have, for example, an olefinic double bond, preferably a polymerizable group selected from vinyl, 1-methylvinyl, allyl, methallyl, acryloyl, methacryloyl, vinyloxy, 1-methylvinyloxy, allyloxy, methallyloxy, acryloyloxy, and methacryloyloxy groups.

[0061] The polymerizable compound other than the polymerizable compound having an aromatic heterocycle may be, for example, a polyfunctional compound having an acyclic structure, a polyfunctional compound having a hydrocarbon ring, or a monofunctional compound. These polymerizable compounds may be used alone or in combination of two or more.

[0062] Examples of the polyfunctional compound having an acyclic structure include compounds having two or more (meth)acryloyl groups.

[0063] Examples of bifunctional compounds having an acyclic structure include di(meth)acrylates of alkylene glycols having 1 to 40 carbon atoms in which the methylene group may be substituted 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 (meth)acrylate, 1,9-nonanediol (meth)acrylate, 1,10-decanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; and 2-(2-vinyloxyethoxy)ethyl acrylate.

[0064] Examples of the trifunctional or higher-functional compound having an acyclic structure include esters of a diol having 4 to 40 carbon atoms, which may 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.

[0065] Examples of the polyfunctional compound having a hydrocarbon ring include compounds having two or more (meth)acryloyl groups.

[0066] Examples of bifunctional compounds having a hydrocarbon ring include 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 groups 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.

[0067] Examples of trifunctional or higher-functional compounds having a hydrocarbon ring include ethoxylated isocyanuric acid tri(meth)acrylate and ε-caprolactone-modified tri-(2-acryloylethyl)isocyanurate.

[0068] Examples of the monofunctional compound 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 ethyldiethylene glycol (meth)acrylate; monofunctional compounds having a hydrocarbon ring, such as dicyclopentadiene (meth)acrylate, isobornyl (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.

[0069] When the curable composition contains a polymerizable compound other than a polymerizable compound having an aromatic heterocycle, the content of the polymerizable compound having an aromatic heterocycle may be, for example, 5% by mass or more, 20% by mass or more, or 30% by mass or more, based on the total mass of the polymerizable compound. The content of the polymerizable compound having an aromatic heterocycle may be, for example, 80% by mass or less, 75% by mass or less, or 65% by mass or less, based on the total mass of the polymerizable compound. The content of the polymerizable compound having an aromatic heterocycle may be, for example, 5 to 80% by mass, 20 to 75% by mass, or 30 to 65% by mass, based on the total mass of the polymerizable compound.

[0070] In the curable composition, the total mass of the polymerizable compound (the sum of the mass of the polymerizable compound having an aromatic heterocycle and the mass of other polymerizable compounds) can be, for example, 80% by mass or less, 75% by mass or less, or 70% by mass or less, based on the total mass of the curable composition. The lower the content of the polymerizable compound, the higher the refractive index of the film obtained from the curable composition, and the efficiency of light extraction from the light-emitting layer is improved. The content of the polymerizable compound can be, for example, 20% by mass or more, 30% by mass or more, or 40% by mass or more.

[0071] <Inorganic fine particles>

[0072] The curable composition of this embodiment contains inorganic particles. The inorganic particles 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, the higher the refractive index of the film obtained from the curable composition, and the efficiency of light extraction from the light-emitting 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 above refractive index is the value under the sodium D line. It should be noted that in this application specification, the refractive index refers to the refractive index at 550nm.

[0073] The inorganic fine particles may be either oxides or nitrides. Examples of the inorganic fine particles include TiO2 (titanium oxide, refractive index 2.3-2.7), 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 1.9-2.0), 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), and TiN (titanium nitride, refractive index 1.6).

[0074] As the inorganic fine particles, oxides of elements from Groups 3 to 5 and 12 to 15 of the periodic table or nitrides of elements from Group 4 of the periodic table are preferred, with titanium oxide, zirconium oxide, aluminum oxide, niobium oxide, and silicon nitride being more preferred, and titanium oxide and zirconium oxide being even more preferred. The inorganic fine particles may be used alone or in combination of two or more.

[0075] The volume average particle size of the inorganic particles is, for example, 100 nm or less, preferably 50 nm or less, and more preferably 30 nm or less. The smaller the particle size, the more the visible light transmittance of the obtained film can be improved. The lower limit of the volume average particle size of the inorganic particles (A) is not particularly limited, and for example, it is 0.1 nm or more, preferably 0.5 nm or more, and more preferably 1.0 nm or more.

[0076] The content of the inorganic fine particles is, for example, 10% by mass or greater, preferably 12% by mass or greater, and more preferably 15% by mass or greater, based on the total mass of the curable composition. The higher the content of the inorganic fine particles, the higher the refractive index of the film obtained from the curable composition, and the efficiency of light extraction from the light-emitting layer is improved. The content of the inorganic fine particles is, for example, 60% by mass or less, preferably 40% by mass or less, and more preferably 30% by mass or less, based on the total mass of the curable composition.

[0077] The inorganic fine particles may be surface treated with a coupling agent. Examples of the coupling agent include silane coupling agents, zirconium coupling agents, titanium coupling agents, and phosphorus coupling agents. One coupling agent may be used alone or in combination of two or more.

[0078] 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.

[0079] 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, monoalkoxyaluminum zirconate, trialkoxyaluminum zirconate, and tetraalkoxyaluminum zirconate.

[0080] Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl tristearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryloyl isostearyl titanate, isopropyl tri(dodecylbenzenesulfonyl) titanate, isopropyl isostearyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, and isopropyl triisostearate titanate.

[0081] Examples of the phosphorus coupling agent include isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(ditidecyl phosphite) titanate, tetrakis(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, bis(dioctyl pyrophosphate)oxyacetate phthalate, bis(dioctyl pyrophosphate)ethylene titanate, and acryloyloxyethylphthaloyloxyethyl diethyl phosphate.

[0082] The inorganic fine particles are contained in the curable composition together with a dispersant, for example. As the dispersant, any type of dispersant such as a nonionic, anionic, or cationic dispersant may be used, with anionic dispersants being preferred. As the anionic dispersant, a phosphate dispersant may be preferably used.

[0083] 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).

[0084] The amount of dispersant is, for example, more than 1 mass part, preferably more than 5 mass parts, more preferably more than 10 mass parts relative to inorganic particles 100 mass parts. The more the amount of dispersant becomes, the more the dispersibility of inorganic particles can be improved. In addition, the amount of dispersant is, for example, less than 100 mass parts, preferably less than 60 mass parts, more preferably less than 40 mass parts, relative to inorganic particles 100 mass parts. The less the amount of dispersant becomes, the more the refractive index of curable composition can be improved.

[0085] <Compound represented by formula (I)>

[0086] The curable composition of this embodiment contains the compound represented by formula (I).

[0087]

[0088] In formula (I), R N1 、R N2 and R N3 Each of them independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a group represented by the following formula (II), R N1 、R N2 and R N3 At least one of them is a saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by the following formula (II), R N1 、R N2 and R N3 Two of them can bond to each other to form a ring.

[0089]

[0090] [In formula (II), Q represents a group that forms an aromatic hydrocarbon ring having 6 to 20 carbon atoms together with 3 carbon atoms.]

[0091] As R N1 、R N2 and R N3 Examples of the saturated hydrocarbon group include an alkyl group and a cycloalkyl group.

[0092] Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isobutyl, butyl, tert-butyl, hexyl, heptyl, octyl, nonyl, decyl, heptadecyl, and undecyl. The alkyl group having 1 to 20 carbon atoms may have a cycloalkyl group having 3 to 8 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms having a cycloalkyl group having 3 to 8 carbon atoms include cycloalkylmethyl and dicyclopentylmethyl.

[0093] The cycloalkyl group having 1 to 20 carbon atoms may be monocyclic or polycyclic and may be condensed. Examples thereof include cyclopentyl, cyclohexyl, dicyclopentenyl, and decahydronaphthyl.

[0094] From the viewpoint of further improving storage stability, as R N1 、R N2 and R N3 A saturated hydrocarbon group, preferably an alkyl group.

[0095] Examples of the group represented by formula (II) include a phenyl group, a naphthyl group, and an anthracenyl group.

[0096] From the viewpoint of further improving storage stability, the group represented by formula (II) is preferably a phenyl group.

[0097] Specific examples of the compound represented by formula (I) include butylamine, pentylamine, cyclopentylamine, aniline, diethylamine, dipropylamine, N-methylaniline, triethylamine, tributylamine, N,N-diisopropylethylamine (DIPEA), tri-n-octylamine (TOA), and N,N-dimethylaniline.

[0098] As the compound represented by formula (I), R N1 、R N2 and R N3 All of them are independently preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 12 carbon atoms, and still more preferably an alkyl group having 1 to 10 carbon atoms.

[0099] From the perspective of further improving storage stability, the content of the compound represented by formula (I) can be, for example, 0.001 mol% or more, 0.01 mol% or more, 0.1 mol% or more, or 0.15 mol% or more, based on the total amount of the polymerizable compound having an aromatic heterocycle. From the perspective of film recovery when a cured film is formed, the content of the compound represented by formula (I) can be, for example, 80 mol% or less, 50 mol% or less, 20 mol% or less, 10 mol% or less, 6.5 mol% or less, or 5.0 mol% or less, based on the total amount of the polymerizable compound having an aromatic heterocycle. From these viewpoints, based on the total amount of the polymerizable compound having an aromatic heterocycle, the content of the compound represented by formula (I) can be, for example, 0.001 to 80 mol%, 0.001 to 50 mol%, 0.001 to 20 mol%, 0.01 to 10 mol%, 0.1 to 50 mol%, 0.1 to 20 mol%, 0.1 to 10 mol%, 0.1 to 6.5 mol%, or 0.15 to 5.0 mol%.

[0100] In the curable composition, based on the total mass of the curable composition, the content of the compound shown in formula (I) can be, for example, 25% by mass or less, 15% by mass or less, or 10% by mass or less. Based on the total mass of the curable composition, the content of the compound shown in formula (I) can be, for example, 0.0001% by mass or more, 0.001% by mass or more, 0.01% by mass or more, or 0.1% by mass or more. From these viewpoints, based on the total mass of the curable composition, the content of the compound shown in formula (I) can be, for example, 0.0001 to 25% by mass, 0.001 to 25% by mass, 0.01 to 15% by mass, or 0.1 to 10% by mass or less.

[0101] <Polymerization initiator>

[0102] The curable composition of this embodiment contains a polymerization initiator. Polymerization initiators utilize light or heat to generate active free radicals, acids, and the like. While any compound capable of initiating polymerization is not particularly limited, photopolymerization initiators are preferred. Examples of polymerization initiators that generate active free radicals include O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, phosphinate compounds, and biimidazole compounds. One polymerization initiator may be used alone, or two or more may be used in combination.

[0103] The O-acyl oxime compound is a compound having a partial structure represented by formula (c1): Hereinafter, * represents a bonding site.

[0104]

[0105] Examples of the O-acyl oxime compounds 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-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine. 1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethoxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02, and OXE03 (all manufactured by BASF); and ADEKA ARKLS (registered trademark) N-1919, NCI-831, and NCI-930 (manufactured by ADEKA) can be used.

[0106] 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.

[0107]

[0108] Examples of the compound 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, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) can be used.

[0109] 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-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal.

[0110] 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, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine.

[0111] 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) can be used.

[0112] Examples of the phosphinate compound include ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate, and commercially available products such as Omnirad TPO-L (manufactured by IGM Resins BV) can be used.

[0113] 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'-tetra(alkoxyphenyl)biimidazole, 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, Japanese Patent Application Laid-Open No. 7-10913).

[0114] As the polymerization initiator, 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 can also be used.

[0115] The polymerization initiator may also contain an acid generator. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, and diphenyl iodide. p-Toluenesulfonate, diphenyliodonium Hexafluoroantimonate, etc. salts, nitrobenzyl tosylate salts and benzoin tosylate salts.

[0116] The polymerization initiator preferably comprises at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, phosphinate compounds, and biimidazole compounds, more preferably comprises at least one selected from the group consisting of acylphosphine oxide compounds and phosphinate compounds, and even more preferably a phosphinate compound.

[0117] When the polymerization initiator contains at least one selected from an acylphosphine oxide compound and a phosphinate compound, the total content of the acylphosphine oxide compound and the phosphinate compound is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and may be 100% by mass, based on the total mass of the polymerization initiator.

[0118] The content of the polymerization initiator relative to 100 parts by mass of the total amount of the polymerizable compound 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.

[0119] <Other ingredients>

[0120] The curable composition of the present embodiment may contain a resin, a solvent, a surfactant, an antioxidant, a light stabilizer, and the like as needed.

[0121] (Method for producing curable composition)

[0122] The curable composition of the present embodiment can be produced by mixing, for example, a polymerizable compound having an aromatic heterocycle, inorganic fine particles, a compound represented by formula (I), a polymerization initiator, and other components as needed.

[0123] (Cured film and method for producing the same)

[0124] The cured film of the present embodiment is formed from the above-mentioned curable composition.

[0125] The cured film can be produced by treating the curable composition using a wet method such as spin coating, casting, microgravure coating, gravure coating, rod coating, roll coating, wire bar coating, dip coating, spray coating, screen printing, flexographic printing, offset printing, inkjet printing, capillary coating, or nozzle coating. A patterned cured film can also be produced using photolithography, inkjet printing, or the like.

[0126] The thickness of the cured film is usually 100 μm or less, preferably 1 μm to 50 μm.

[0127] The cured film can be used as a microlens, a sealing material, and the like, and is particularly preferably used as a microlens, a sealing material, and the like for a light-emitting element.

[0128] Example

[0129] The present invention will be further specifically described below with reference to Examples. However, the present invention is not limited to the following Examples and can be implemented with appropriate modifications within the scope of the above and below principles. Such modifications are within the technical scope of the present invention. It should be noted that, unless otherwise specified, "parts" refer to "parts by mass" and "%" refers to "% by mass."

[0130] (Example 1)

[0131] [Manufacturing of Inorganic Microparticle Dispersion]

[0132] 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, zirconium oxide volume average particle size: 10 nm). 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 amount of residual methyl ethyl ketone was confirmed by gas chromatography (GC) analysis, and no residual methyl ethyl ketone was detected.

[0133] [Preparation of Curable Composition]

[0134] The inorganic fine particle dispersion was prepared by mixing 24 parts by mass of zirconium oxide particles, 6 parts by mass of a dispersant, 31 parts by mass of benzyl acrylate (BzA), 20 parts by mass of 9-vinylcarbazole (VCz) (manufactured by Nisshoku Fine Chemical Co., Ltd.), 5 parts by mass of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA, manufactured by Nippon Shokubai Co., Ltd., hereinafter referred to as VEEA), and 6 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as A-9550). Phenyl (2,4,6-trimethylbenzoyl) ethyl phosphinate (Omnirad TPO-L, IGM Resins) as a polymerization initiator was added. 8 parts by mass of TPO-L (manufactured by BV Co., Ltd., hereinafter also referred to as TPO-L) and 0.01 parts by mass of N,N-diisopropylethylamine (DIPEA) (manufactured by Tokyo Chemical Industry Co., Ltd.) as a compound represented by formula (I) were dissolved therein, and the mixture was filtered through a PTFE membrane filter to obtain a curable composition.

[0135] (Example 2)

[0136] A curable composition was obtained in the same manner as in Example 1 except that the amount of N,N-diisopropylethylamine (DIPEA) was changed to 0.05 parts by mass.

[0137] (Example 3)

[0138] A curable composition was obtained in the same manner as in Example 1 except that 0.0274 parts by mass of tri-n-octylamine (TOA) was added as the compound represented by formula (I) instead of N,N-diisopropylethylamine (DIPEA).

[0139] (Example 4)

[0140] A curable composition was obtained in the same manner as in Example 3 except that the blending amount of tri-n-octylamine (TOA) was changed to 0.137 parts by mass.

[0141] (Example 5)

[0142] In the same manner as in Example 1, an inorganic fine particle dispersion was prepared.

[0143] The inorganic fine particle dispersion was prepared in a component ratio such that the mass of zirconium oxide particles was 20.6 parts by mass, the mass of a dispersant was 5.2 parts by mass, the mass of benzyl acrylate (BzA) was 38.2 parts by mass, and the mass of 9-vinylcarbazole (VCz) (manufactured by Nisshoku Fine Chemical Co., Ltd.) was 28 parts by mass. 8 parts by mass of ethyl phenyl (2,4,6-trimethylbenzoyl) phosphinate (Omnirad TPO-L, manufactured by IGM Resins BV) as a polymerization initiator and 0.014 parts by mass of N,N-diisopropylethylamine (DIPEA) (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a compound represented by formula (I), were added and dissolved, and then filtered through a PTFE membrane filter to obtain a curable composition.

[0144] (Example 6)

[0145] A curable composition was obtained in the same manner as in Example 5 except that the amount of N,N-diisopropylethylamine (DIPEA) was changed to 0.07 parts by mass.

[0146] (Example 7)

[0147] A curable composition was obtained in the same manner as in Example 1 except that the amount of N,N-diisopropylethylamine (DIPEA) was changed to 0.001 parts by mass.

[0148] (Example 8)

[0149] A curable composition was obtained in the same manner as in Example 1 except that the amount of N,N-diisopropylethylamine (DIPEA) was changed to 0.1 parts by mass.

[0150] (Example 9)

[0151] A curable composition was obtained in the same manner as in Example 1 except that the amount of N,N-diisopropylethylamine (DIPEA) was changed to 1 part by mass.

[0152] (Example 10)

[0153] A curable composition was obtained in the same manner as in Example 1 except that the amount of N,N-diisopropylethylamine (DIPEA) was changed to 10 parts by mass.

[0154] (Comparative Example 1)

[0155] A comparative curable composition was obtained in the same manner as in Example 1 except that N,N-diisopropylethylamine (DIPEA) was not added.

[0156] (Example 11)

[0157] A curable composition was obtained in the same manner as in Example 1 except that the amount of N,N-diisopropylethylamine (DIPEA) was changed to 2 parts by mass.

[0158] (Example 12)

[0159] A curable composition was obtained in the same manner as in Example 1 except that the amount of N,N-diisopropylethylamine (DIPEA) was changed to 5 parts by mass.

[0160] (Example 13)

[0161] In the same manner as in Example 1, an inorganic fine particle dispersion was prepared.

[0162] The mass of zirconium oxide particles is 24 parts by mass, the mass of a dispersant is 6 parts by mass, the mass of benzyl acrylate (BzA) is 20 parts by mass, the mass of the compound represented by the above formula (B1d-5) (6EDNTA) is 31 parts by mass, the mass of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA, manufactured by Nippon Shokubai Co., Ltd.) is 5 parts by mass, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-955 The inorganic fine particle dispersion was prepared in a manner such that 6 parts by mass of the inorganic fine particle dispersion was added, 8 parts by mass of ADEKAARKLS (registered trademark) NCI-930 (O-acyl oxime compound, manufactured by ADEKA Co., Ltd.) as a polymerization initiator and 0.025 parts by mass of N,N-diisopropylethylamine (DIPEA) (manufactured by Tokyo Chemical Industry Co., Ltd.) as a compound represented by formula (I) were added and dissolved, and then filtered through a PTFE membrane filter to obtain a curable composition.

[0163] (Comparative Example 2)

[0164] A comparative curable composition was obtained in the same manner as in Example 13 except that N,N-diisopropylethylamine (DIPEA) was not added.

[0165] [Evaluation of Curable Composition]

[0166] (Viscosity increase rate)

[0167] Using an E-type viscometer, the rotation speed of the rotor is 10 rpm, and the viscosity of each curable composition obtained in Examples 1 to 12 and Comparative Example 1 at a temperature of 23 ° C is measured, and it is taken as the viscosity at 0 hours. After the obtained curable composition is stored in a dark place at 23 ° C for 1 week, the viscosity of the curable composition is measured under the same conditions as above, and (viscosity after 1 week) / (viscosity at 0 hours) is calculated as the viscosity increase rate. The lower the viscosity increase rate, the better the storage stability of the curable composition. The viscosity increase rate is preferably 1.4 or less, more preferably 1.3 or less, and further preferably 1.2 or less.

[0168] (Viscosity change [visual observation])

[0169] For each curable composition obtained in Example 13 and Comparative Example 2, the viscosity at 23°C was visually confirmed for the sample at 0 hours and the sample after being stored in a dark place at 23°C for 1 week. Specifically, the container containing the sample (23°C) was tilted 45° and the flowability of the sample was visually observed. The less it flowed, the higher the viscosity. The smaller the increase in viscosity compared to the sample at 0 hours, the better the storage stability of the curable composition.

[0170] In the curable composition of Example 13, no difference in viscosity was observed between the sample at 0 hours and the sample after 1 week of storage. In the curable composition of Comparative Example 2, the viscosity of the sample after 1 week of storage increased compared to the sample at 0 hours. In other words, the curable composition of Example 13 had superior storage stability to the curable composition of Comparative Example 2.

[0171] [Production and Evaluation of Cured Film]

[0172] Each of the obtained curable compositions was applied on 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 UV irradiation was performed to obtain a cured film.

[0173] The obtained cured film was subjected to a micro-indentation hardness test (nano-indentation test) to measure the Young's modulus (indentation elastic modulus) E IT and recovery rate (indentation plasticity and elasticity) n IT In this test, the maximum load was adjusted so that the indentation depth was less than 20% of the film thickness so as not to be affected by the glass substrate. Young's modulus (indentation elastic modulus) E IT and recovery rate (indentation plasticity and elasticity) n IT The determination is based on ISO14577-1.

[0174] Table 1 shows the results of Examples and Comparative Examples.

[0175] In addition, the relationship between Strain [nm] (indentation depth) and Load [nm] (test load) of the cured films formed from the curable compositions of Examples 7 to 10 is shown in FIG. Figure 1 The relationship between Strain[nm] (indentation depth) and Load[nm] (test load) is an indicator of the recovery rate of the cured film. In the figure, "DIPEA 0.001 parts" corresponds to Example 7, "DIPEA 0.1 parts" corresponds to Example 8, "DIPEA 1 parts" corresponds to Example 9, and "DIPEA 10 parts" corresponds to Example 10. According to Table 1 and Figure 1 It can be seen that the viscosity increase rate of Example 10 is good, but the recovery rate is reduced to less than 11 (Table 1). For the cured film obtained from Example 10, the recovery of the film is slightly reduced ( Figure 1 ).

[0176] [Table 1]

[0177]

[0178] As apparent from Table 1, the curable compositions of Examples had a lower viscosity increase rate and were superior in storage stability compared to the curable compositions of Comparative Examples.

Claims

1. A curable composition comprising: a polymerizable compound having an aromatic heterocycle, inorganic fine particles, a compound represented by formula (I), and a polymerization initiator. In formula (I), R N1 、R N2 and R N3 Each of them independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a group represented by the following formula (II), R N1 、R N2 and R N3 At least one of them is a saturated hydrocarbon group having 1 to 20 carbon atoms or a group represented by the following formula (II), R N1 、R N2 and R N3 Two of them can bond to each other to form a ring, In formula (II), Q represents a group that forms an aromatic hydrocarbon ring having 6 to 20 carbon atoms together with three carbon atoms.

2. The curable composition according to claim 1, wherein The content of the compound represented by formula (I) is 0.1 mol% or more based on the total amount of the polymerizable compound having an aromatic heterocycle.

3. The curable composition according to claim 1 or 2, wherein The group represented by formula (II) is a phenyl group.

4. The curable composition according to claim 1 or 2, wherein The saturated hydrocarbon group is an alkyl group. 5 . A cured film formed from the curable composition according to claim 1 .

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