WO2022225029A1 - 光硬化性組成物 - Google Patents

光硬化性組成物 Download PDF

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Publication number
WO2022225029A1
WO2022225029A1 PCT/JP2022/018485 JP2022018485W WO2022225029A1 WO 2022225029 A1 WO2022225029 A1 WO 2022225029A1 JP 2022018485 W JP2022018485 W JP 2022018485W WO 2022225029 A1 WO2022225029 A1 WO 2022225029A1
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Prior art keywords
group
groups
solvent
formula
photocurable composition
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PCT/JP2022/018485
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English (en)
French (fr)
Japanese (ja)
Inventor
一樹 浦川
誠太 宮崎
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Tokyo Ohka Kogyo Co Ltd
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Tokyo Ohka Kogyo Co Ltd
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Priority to US18/556,281 priority Critical patent/US20240239922A1/en
Priority to CN202280029505.3A priority patent/CN117178001A/zh
Priority to KR1020237036573A priority patent/KR20230159599A/ko
Priority to EP22791800.0A priority patent/EP4317196A4/en
Publication of WO2022225029A1 publication Critical patent/WO2022225029A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/38—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/12—Esters of phenols or saturated alcohols
    • C08F22/24—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/24—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/38—Amides
    • C08F222/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present invention relates to a photocurable composition, a cured product of the photocurable composition, and a method for forming a cured film using the photocurable composition.
  • high refractive index materials have been used to form optical members.
  • Compositions in which metal oxide particles such as titanium oxide and zirconium oxide are dispersed in an organic component are used as high refractive materials.
  • As a composition for forming such a high refractive material an energy ray containing a metal oxide (A) having a specific particle size, a (meth)acrylate (B), and a photopolymerization initiator (C)
  • a curable composition has been proposed (see Patent Document 1).
  • a cured product having a high refractive index can be formed as described above.
  • higher refractive index materials for high refractive index materials In order to further increase the refractive index, it is effective to increase the amount of metal oxide particles in the curable composition.
  • the metal oxide particles are blended in the curable composition at a high concentration, it is difficult to disperse the metal oxide particles well, or even if the metal oxide particles can be well dispersed, curing There is a problem that the wettability of the adhesive composition to the substrate to be coated is poor.
  • An object of the present invention is to provide a good photocurable composition, a cured product of the photocurable composition, and a method for forming a cured film using the photocurable composition.
  • a photocurable composition containing a photopolymerizable compound (A), metal oxide fine particles (B), an initiator (C), and a solvent (S) contains a photopolymerizable compound ( As A), using a compound having a radically polymerizable group-containing group or a cationically polymerizable group-containing group, having a specific structure containing an oxyalkylene group as a solvent (S), and having a Hildebrand solubility parameter value of
  • the inventors have found that the above problems can be solved by using a plurality of solvents (S1) having a viscosity of 21.0 MPa 0.5 or less, and have completed the present invention.
  • the inventors have found that the above problems can be solved by using a solvent (S1) and another solvent (S2) as the solvent (S) at a predetermined mass ratio, and have completed the present invention. reached.
  • the present invention provides the following.
  • the photopolymerizable compound (A) has a radically polymerizable group-containing group or a cationically polymerizable group-containing group
  • the solvent (S) is represented by the following formula (S1): R S2 -O-(R S1 -O) ns -R S3 (S1) (In formula (S1), R S1 is an alkylene group having 2 to 4 carbon atoms; R S2 and R S3 are each a hydrogen atom, a methyl group, or an ethyl group; R S2 and R S3 is not a hydrogen atom at the same time, and ns is an integer of 1 or more and 4 or less.) including a plurality of solvents (S1) represented by A photocurable composition, wherein the solvent (S1) has a Hildebrand solubility parameter value of 21.0 MPa 0.5 or less.
  • the photopolymerizable compound (A) has an S atom in the center and radically polymerizable group-containing groups at both ends, and the divalent linking portion connecting the center and each end has a substituent
  • the photopolymerizable compound (A) has the radical polymerizable group-containing group
  • the photopolymerizable compound (A) has the following formula (a-1): (In formula (a-1), R 1 and R 2 are each independently a hydrogen atom or a methyl group; R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms; and p and q are each independently 0 or 1.)
  • the photocurable composition according to any one of (1) to (4), comprising a compound represented by:
  • the photopolymerizable compound (A) has the following formula (A1): (In formula (A1), R A1 , R A2 , and R A3 are each independently an organic group, and the organic group as R A1 , the organic group as R A2 , and the organic group as R A3 At least two of the groups have a radically polymerizable group-containing group or a cationically polymerizable group-containing group.)
  • the photocurable composition according to any one of (1) to (5), comprising a compound represented by:
  • the photopolymerizable compound (A) has a radically polymerizable group-containing group or a cationically polymerizable group-containing group
  • the solvent (S) is represented by the following formula (S1): R S2 -O-(R S1 -O) ns -R S3 (S1) (In formula (S1), R S1 is an alkylene group having 2 to 4 carbon atoms; R S2 and R S3 are each a hydrogen atom, a methyl group, or an ethyl group; R S2 and R S3 is not a hydrogen atom at the same time, and ns is an integer of 1 or more and 4 or less.)
  • the mass ratio ((S1):(S2)) of the solvent (S1) and the solvent (S2) is
  • a photocurable composition in which the metal oxide fine particles are well dispersed even when the metal oxide fine particles are contained at a high concentration, and which exhibits good wettability with respect to a substrate to be coated;
  • a cured product of the photocurable composition and a method for forming a cured film using the photocurable composition can be provided.
  • the photocurable composition contains a photopolymerizable compound (A), metal oxide fine particles (B), an initiator (C), and a solvent (S).
  • the photopolymerizable compound (A) is a compound having a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
  • the solvent (S) includes a plurality of solvents (S1) having a specific structure containing an oxyalkylene group and a Hildebrand solubility parameter value of 21.0 MPa 0.5 or less. The solvent (S1) will be described later in detail.
  • the metal oxide fine particles (B) are photocurable. It disperses well in the composition and has good wettability to the substrate to which the photocurable composition is applied.
  • the essential or optional components that the photocurable composition may contain are described below.
  • the photocurable composition contains a photopolymerizable compound (A) as a curable component.
  • the photopolymerizable compound (A) is a compound having a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
  • a radically polymerizable group-containing group typically includes a group containing an ethylenically unsaturated double bond.
  • alkenyl group-containing groups including alkenyl groups such as vinyl groups and allyl groups are preferred, and (meth)acryloyl group-containing groups are more preferred.
  • Examples of cationic polymerizable group-containing groups typically include epoxy group-containing groups, oxetanyl group-containing groups, vinyloxy group-containing groups, and the like. Among these, an epoxy group-containing group and a vinyloxy group-containing group are preferred.
  • the epoxy group-containing group is preferably an alicyclic epoxy group-containing group or a glycidyl group.
  • the alicyclic epoxy group is an aliphatic cyclic group in which two carbon atoms as adjacent ring-constituting atoms in the aliphatic cyclic group are bonded through an oxygen atom. That is, an alicyclic epoxy group has an epoxy group containing a three-membered ring consisting of two carbon atoms and one oxygen atom on an aliphatic ring.
  • (meth)acrylic means both acrylic and methacrylic
  • (meth)acryloyl means both acryloyl and methacryloyl
  • (meth)acrylate is Both acrylates and methacrylates are meant.
  • the photopolymerizable compound (A) When the photopolymerizable compound (A) has a radically polymerizable group-containing group, the photopolymerizable compound (A) is a monofunctional compound having one radically polymerizable group, even if two or more radical polymerization A polyfunctional compound having a functional group may be used, and a polyfunctional compound is preferred.
  • the photopolymerizable compound (A) having a radically polymerizable group-containing group is preferably a compound having one or more (meth)acryloyl groups such as a (meth)acrylate compound or a (meth)acrylamide compound, and one or more (meth)acryloyl groups. ) A (meth)acrylate compound having an acryloyl group is more preferred.
  • Monofunctional compounds having radically polymerizable group-containing groups include, for example, (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxy Methyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic anhydride citraconic acid, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Cyclohexyl (meth) acrylate
  • Polyfunctional compounds having radically polymerizable group-containing groups include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di( meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, trimethylolpropane tri(meth)acrylate ) acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipent
  • photopolymerizable compounds (A) having a radically polymerizable group-containing group trifunctional or higher polyfunctional compounds are preferred, and tetrafunctional or higher polyfunctional compounds are preferred in view of the tendency to increase the strength of the cured product. More preferred are polyfunctional compounds having a functionality of 5 or more.
  • the photocurable composition contains the metal oxide fine particles (B), depending on the composition of the photocurable composition, the metal oxide fine particles (B ) and a layer poor in the metal oxide particles (B) may occur.
  • the photocurable composition is represented by the following formula (A1) or the following formula (A2) as the photopolymerizable compound (A) having a radically polymerizable group-containing group.
  • MA is each independently a (meth)acryloyl group
  • X is each independently an oxygen atom, —NH—, or —N(CH 3 )—
  • R a1 is independently an ethane-1,2-diyl group, a propane-1,2-diyl group, or a propane-1,3-diyl group
  • R a2 is a hydroxyl group
  • na1 and na2 are each independently 0 or 1.
  • the alkyl group having 1 to 4 carbon atoms as R a2 includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl groups.
  • a methyl group and an ethyl group are preferred.
  • Preferred examples of the compound represented by formula (A1) and the compound represented by formula (A2) include pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth) Acrylate, glycerin tri(meth)acrylate, and compounds 1) to 32) below.
  • MA is a (meth)acryloyl group.
  • the mass of the compound represented by the formula (A1) and the mass of the compound represented by the formula (A2) with respect to the mass of the photopolymerizable compound (A) is preferably 20% by mass or more and 70% by mass or less, more preferably 30% by mass or more and 70% by mass or less, and even more preferably 40% by mass or more and 70% by mass or less.
  • the photocurable composition has an S atom at the center as the photopolymerizable compound (A) having a radically polymerizable group-containing group, and radical polymerization at both ends. It preferably contains a compound having an aromatic ring and an S atom, which may have a substituent, in the divalent linking portion linking the center and each end, and at both ends (meta ) having an acryloyl group and containing a compound having a diphenylsulfide skeleton as a combination of a central S atom and an aromatic ring constituting a divalent linking portion, represented by the following formula (a-1): More preferably it contains a compound.
  • R 1 and R 2 are each independently a hydrogen atom or a methyl group.
  • R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms.
  • p and q are each independently 0 or 1;
  • aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring and phenanthroline ring; furan ring, pyrrole ring, thiophene ring, pyridine ring, thiazole ring and benzothiazole ring; Aromatic heterocycle; Among them, a benzene ring (eg, 1,4-phenyl group, etc.) is preferred.
  • substituents at the connecting portion include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylamino group, a dialkylamino group, an alkylamide group, an alkenyl group, an alkynyl group, a halogen atom, and a cyano groups, nitro groups, alkylthiol groups, and N-alkylcarbamate groups.
  • an alkyl group is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
  • R 1 and R 2 are each independently a hydrogen atom or a methyl group. R 1 and R 2 may be different from each other or may be the same. R 1 and R 2 are preferably the same because the compound represented by formula (a-1) is easily synthesized and available.
  • R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms. R 3 and R 4 may be different from each other or may be the same. It is preferable that R 3 and R 4 are the same because the compound represented by formula (a-1) is easily synthesized and available.
  • the alkyl group having 1 to 5 carbon atoms as R 3 and R 4 may be linear or branched.
  • alkyl groups having 1 to 5 carbon atoms as R 3 and R 4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group and tert-pentyl group.
  • Preferred specific examples of the compound represented by formula (a-1) include the following compounds.
  • the photocurable composition contains a compound represented by formula (a-1) as a photopolymerizable compound (A) having a radically polymerizable group-containing group
  • the formula for the mass of the photopolymerizable compound (A) is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, even more preferably 70% by mass or more, and 100% by mass. Especially preferred.
  • the photocurable composition has a radically polymerizable group-containing group as the photopolymerizable compound (A) in the following formula (A3) It preferably contains the sulfur-containing (meth)acrylate represented.
  • Ar a1 -R a21 -SR a22 -O-CO-CR a23 CH 2 (A3)
  • Ar a1 is a phenyl group optionally substituted with a halogen atom
  • R a21 is a single bond or an alkylene group having 1 to 6 carbon atoms
  • R a22 is an alkylene group having 1 to 6 carbon atoms
  • R a23 is a hydrogen atom or a methyl group.
  • Ar a1 is a phenyl group optionally substituted with a halogen atom.
  • the number of halogen atoms bonded to the phenyl group is not particularly limited.
  • the number of halogen atoms bonded to the phenyl group is preferably 1 or 2, more preferably 1.
  • the plurality of halogen atoms bonded to the phenyl group may consist of the same kind of halogen atoms alone, or may consist of two or more kinds of halogen atoms.
  • a halogen atom that can be bonded to a phenyl group includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom, a chlorine atom, and a bromine atom being preferred.
  • Ar a1 is preferably an unsubstituted phenyl group.
  • R a21 is a single bond or an alkylene group having 1 to 6 carbon atoms.
  • alkylene group having 1 to 6 carbon atoms include methylene group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group and butane-1,4-diyl group. pentane-1,5-diyl group, and hexane-1,6-diyl group.
  • R a21 is preferably a single bond and a methylene group, more preferably a single bond.
  • R a22 is an alkylene group having 1 to 6 carbon atoms.
  • the alkylene group having 1 to 6 carbon atoms include methylene group, ethane-1,2-diyl group, propane-1,2-diyl group, propane-1,3-diyl group and butane-1,4-diyl group. pentane-1,5-diyl group, and hexane-1,6-diyl group.
  • R a22 is preferably a methylene group, an ethane-1,2-diyl group and a propane-1,3-diyl group, more preferably an ethane-1,2-diyl group and a propane-1,3-diyl group.
  • Ar a1 is a phenyl group and R a21 is a single group.
  • a bond is particularly preferred.
  • sulfur-containing (meth)acrylates represented by formula (A3) include 2-phenylthioethyl (meth)acrylate, 3-phenylthiopropyl (meth)acrylate, 2-benzylthioethyl (meth) Acrylates, 3-benzylthiopropyl (meth)acrylate, 2-(2-chlorophenyl)ethyl (meth)acrylate, 2-(3-chlorophenyl)ethyl (meth)acrylate, 2-(4-chlorophenyl)ethyl (meth)acrylate , 3-(2-chlorophenyl)propyl (meth)acrylate, 3-(3-chlorophenyl)propyl (meth)acrylate, 3-(4-chlorophenyl)propyl (meth)acrylate, 2-(2-fluorophenyl)ethyl ( meth)acrylate, 2-(3-fluorophenyl)ethyl (meth)acrylate,
  • the photocurable composition contains a sulfur-containing (meth)acrylate represented by formula (A3) as a photopolymerizable compound (A) having a radically polymerizable group-containing group
  • the mass of the photopolymerizable compound (A) is preferably 40% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 100% by mass or less, 70% by mass or more and 100% by mass % or less is more preferable, and 80% by mass or more and 100% by mass or less is particularly preferable.
  • the photopolymerizable compound (A) may be a monofunctional compound having one cationically polymerizable group, or two or more cationic polymerizations.
  • a polyfunctional compound having a functional group may be used, and a polyfunctional compound is preferred.
  • the photocurable composition may contain a vinyl ether compound as the photopolymerizable compound (A).
  • vinyl ether compounds may be monofunctional compounds or polyfunctional compounds.
  • vinyl ether compounds include vinylphenyl ether, 4-vinyloxytoluene, 3-vinyloxytoluene, 2-vinyloxytoluene, 1-vinyloxy-4-chlorobenzene, 1-vinyloxy-3-chlorobenzene, 1- vinyloxy-2-chlorobenzene, 1-vinyloxy-2,3-dimethylbenzene, 1-vinyloxy-2,4-dimethylbenzene, 1-vinyloxy-2,5-dimethylbenzene, 1-vinyloxy-2,6-dimethylbenzene, 1-vinyloxy-3,4-dimethylbenzene, 1-vinyloxy-3,5-dimethylbenzene, 1-vinyloxynaphthalene, 2-vinyloxynaphthalene, 2-vinyloxyfluorene, 3-vinyloxyfluorene, 4-vinyloxy- Aromatic monovinyl ether compounds such as 1,1′-biphenyl,
  • the photocurable composition may contain various epoxy compounds as the photopolymerizable compound (A).
  • epoxy compounds include bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin; type epoxy resin, brominated phenol novolac type epoxy resin, ortho-cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, and bisphenol AD novolac type epoxy resin; Cycloaliphatic epoxy resins; aromatic epoxy resins such as epoxides of naphthalene-type phenol resins; glycidyl ester-type epoxy resins such as dimer acid glycidyl esters and triglycidyl esters; tetraglycidylaminodiphenylmethane, t
  • oligomeric or polymeric polyfunctional epoxy compounds can also be preferably used.
  • Typical examples of oligomeric or polymeric polyfunctional epoxy compounds include phenolic novolac type epoxy compounds, brominated phenolic novolac type epoxy compounds, orthocresol novolac type epoxy compounds, xylenol novolac type epoxy compounds, naphthol novolak type epoxy compounds, Bisphenol A novolak type epoxy compounds, bisphenol AD novolac type epoxy compounds, epoxidized dicyclopentadiene type phenol resins, epoxidized naphthalene type phenol resins, and the like can be mentioned.
  • Another example of a suitable epoxy compound is a polyfunctional alicyclic epoxy compound having an alicyclic epoxy group.
  • alicyclic epoxy compounds include 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane and bis(3,4-epoxycyclohexylmethyl)adipate , bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3′,4′-epoxy-6′-methylcyclohexanecarboxylate, ⁇ -caprolactone modification 3, 4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, ⁇ -methyl- ⁇ -valerolactone-modified 3, 4-epoxycyclohexylmethyl-3′,4′-epoxy
  • alicyclic epoxy compounds represented by the following formulas (a01-1) to (a01-5) are preferable because they give cured products with high hardness.
  • Z 01 represents a single bond or a linking group (a divalent group having one or more atoms).
  • R a01 to R a018 each independently represent a hydrogen atom, a halogen atom, and It is a group selected from the group consisting of organic groups.
  • the linking group Z 01 includes, for example, a divalent hydrocarbon group, —O—, —O—CO—, —S—, —SO—, —SO 2 —, —CBr 2 —, —C(CBr 3 ) 2 -, -C(CF 3 ) 2 -, and -R a019 -O-CO-, a divalent group selected from the group consisting of a group consisting of a plurality of such groups, and the like.
  • Examples of the divalent hydrocarbon group that is the linking group Z01 include a linear or branched alkylene group having from 1 to 18 carbon atoms, a divalent alicyclic hydrocarbon group, and the like. can be done.
  • Examples of linear or branched alkylene groups having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, dimethylene and trimethylene groups.
  • divalent alicyclic hydrocarbon group examples include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3- Cycloalkylene groups (including cycloalkylidene groups) such as a cyclohexylene group, a 1,4-cyclohexylene group and a cyclohexylidene group can be mentioned.
  • R a019 is an alkylene group having 1 to 8 carbon atoms, preferably a methylene group or an ethylene group.
  • R a01 to R a018 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
  • R a02 and R a010 may be bonded to each other.
  • R a013 and R a016 may combine with each other to form a ring, and m a1 is 0 or 1.
  • the alicyclic epoxy compound represented by the above formula (a01-2) is represented by the following formula (a01-2-1), which corresponds to a compound in which m a1 in the above formula (a01-2) is 0. are preferred.
  • R a01 to R a012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
  • R a02 and R a010 are bonded to each other to form a ring; may form.
  • R a01 to R a010 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
  • R a02 and R a08 may be bonded to each other.
  • R a01 to R a012 are groups selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group.
  • R a02 and R a010 may be bonded to each other.
  • R a01 to R a012 are groups selected from the group consisting of hydrogen atoms, halogen atoms, and organic groups.
  • R a01 to R a018 are organic groups
  • the organic groups are not particularly limited as long as they do not hinder the object of the present invention. , a group consisting of a carbon atom and a halogen atom, or a group containing a heteroatom such as a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom in addition to a carbon atom and a hydrogen atom.
  • halogen atoms include chlorine, bromine, iodine, and fluorine atoms.
  • the organic group includes a hydrocarbon group, a group consisting of a carbon atom, a hydrogen atom, and an oxygen atom, a halogenated hydrocarbon group, a group consisting of a carbon atom, an oxygen atom, and a halogen atom, a carbon atom, and a hydrogen atom. , an oxygen atom and a halogen atom are preferred.
  • the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group containing an aromatic skeleton and an aliphatic skeleton.
  • the number of carbon atoms in the organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 5 or less.
  • hydrocarbon groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl group.
  • n-heptyl group, n-octyl group 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group , n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and chain alkyl groups such as n-icosyl group; vinyl group, 1-propenyl group, 2-n-propenyl group (allyl group), 1-n -chain alkenyl groups such as butenyl group, 2-n-butenyl group, and 3-n-butenyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclo
  • halogenated hydrocarbon groups include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2 , 2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, and Halogenated chain alkyl groups such as perfluorodecyl group; 2-chlorocyclohexyl group, 3-chlorocyclohexyl group, 4-chlorocyclohexyl group, 2,4-dichlorocyclohexyl group, 2-bromocyclohexyl group, 3-bromo
  • groups consisting of carbon atoms, hydrogen atoms, and oxygen atoms include hydroxy chain groups such as hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, and 4-hydroxy-n-butyl group.
  • R a01 to R a018 are each independently preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms, All of R a01 to R a018 are more preferably hydrogen atoms, since a cured film having particularly excellent mechanical properties can be easily formed.
  • R a01 to R a018 are the same as R a01 to R a018 in formula (a01-1).
  • the divalent group formed when R a02 and R a08 are bonded to each other includes, for example, —CH 2 — and —C(CH 3 ) 2 —.
  • alicyclic epoxy compounds represented by formula (a01-2) specific examples include alicyclic epoxy compounds represented by formula (a01-2a) and formula (a01-2b) below. compound.
  • alicyclic epoxy compounds represented by formula (a01-3) specific examples include S-spiro[3-oxatricyclo[3.2.1.0 2,4 ]octane-6 , 2′-oxirane] and the like.
  • alicyclic epoxy compounds represented by formula (a01-4) specific examples include 4-vinylcyclohexene dioxide, dipentene dioxide, limonene dioxide, 1-methyl-4-(3 -methyloxiran-2-yl)-7-oxabicyclo[4.1.0]heptane and the like.
  • alicyclic epoxy compounds represented by formula (a01-5) specific examples include 1,2,5,6-diepoxycyclooctane and the like.
  • X a1 , X a2 and X a3 are each independently a hydrogen atom or an organic group which may contain an epoxy group, and X a1 , X a2 and X a3 has 2 or more epoxy groups.
  • R a20 to R a22 are linear, branched or cyclic alkylene groups, arylene groups, —O—, —C( ⁇ O)—, —NH— and these It is a combination of groups, each of which may be the same or different, and E 1 to E 3 are an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilyl group, an isocyanate group, and a blocked isocyanate.
  • R a20 and E 1 , R a21 and E 2 , and R a22 and E 3 are each represented by the following formula (a1-IIa). and more preferably each of them is a group represented by the following formula (a1-IIa).
  • a plurality of groups represented by formula (a1-IIa) that bind to one compound are preferably the same group.
  • L and C a may combine to form a cyclic structure.
  • the linear, branched or cyclic alkylene group for L is preferably an alkylene group having 1 to 10 carbon atoms, and the arylene group for L is An arylene group having from 5 to 10 carbon atoms is preferred.
  • Examples of compounds represented by formula (a1-II) are shown below as epoxy compounds having an oxiranyl group or an alicyclic epoxy group, but are not limited to these.
  • siloxane compound having two or more glycidyl groups or alicyclic epoxy groups in the molecule
  • siloxane compound a siloxane compound having two or more glycidyl groups or alicyclic epoxy groups in the molecule
  • a siloxane compound is a compound having a siloxane skeleton composed of siloxane bonds (Si—O—Si) and two or more glycidyl groups or alicyclic epoxy groups in the molecule.
  • siloxane skeleton in the siloxane compound examples include a cyclic siloxane skeleton and a cage-type or ladder-type polysilsesquioxane skeleton.
  • siloxane compound among others, a compound having a cyclic siloxane skeleton represented by the following formula (a1-III) (hereinafter sometimes referred to as “cyclic siloxane”) is preferable.
  • R a24 and R a25 each represent a monovalent group containing an epoxy group or an alkyl group. However, at least two of x1 R a24 and x1 R a25 in the compound represented by formula (a1-III) are monovalent groups containing an epoxy group. Also, x1 in formula (a1-III) represents an integer of 3 or more. R a24 and R a25 in the compound represented by formula (a1-III) may be the same or different. Moreover, a plurality of R a24 may be the same or different. A plurality of R a25 may be the same or different.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms, particularly preferably 1 or more carbon atoms). 3 or less) Linear or branched alkyl groups can be mentioned.
  • x1 in the formula (a1-III) represents an integer of 3 or more, and an integer of 3 or more and 6 or less is preferable from the viewpoint of excellent cross-linking reactivity when forming a cured film.
  • the number of epoxy groups in the molecule of the siloxane compound is 2 or more, preferably 2 or more and 6 or less, particularly preferably 2 or more and 4 or less, from the viewpoint of excellent cross-linking reactivity when forming a cured film. is.
  • Examples of the monovalent group containing an epoxy group include an alicyclic epoxy group and a glycidyl ether group represented by -D A -OR a26
  • D A represents an alkylene group and R a26 represents a glycidyl group.
  • R a26 represents a glycidyl group.
  • the D A (alkylene group) includes, for example, a linear or branched alkylene group having 1 to 18 carbon atoms, such as a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, and a trimethylene group. etc. can be mentioned.
  • D 1 and D 2 each independently represent an alkylene group, and ms represents an integer of 0 or more and 2 or less.
  • the photocurable composition includes, as an epoxy compound, in addition to the siloxane compound represented by formula (a1-III), an alicyclic epoxy group-containing cyclic siloxane, and an alicyclic epoxy described in JP-A-2008-248169.
  • Group-containing silicone resins and compounds having a siloxane skeleton such as organopolysilsesquioxane resins having at least two epoxy functional groups in one molecule described in JP-A-2008-19422. good.
  • siloxane compounds include cyclic siloxanes having two or more glycidyl groups in the molecule represented by the following formula.
  • siloxane compound for example, trade names "X-40-2670”, “X-40-2701”, “X-40-2728”, “X-40-2738”, “X-40-2740” (Above, manufactured by Shin-Etsu Chemical Co., Ltd.) and other commercially available products can be used.
  • the photocurable composition preferably contains a compound represented by the following formula (A-1) as the photopolymerizable compound (A), since a cured product with a high refractive index can be easily obtained.
  • A-1 a compound represented by the following formula (A-1) as the photopolymerizable compound (A), since a cured product with a high refractive index can be easily obtained.
  • R A1 , R A2 , and R A3 are each independently an organic group, and the organic group as R A1 , the organic group as R A2 , and the organic group as R A3 At least two of them have a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
  • Preferred examples of the compound represented by formula (A-1) include the compound represented by formula (A-1a) below.
  • R A01 is an optionally substituted quinolinyl group, an optionally substituted isoquinolinyl group, or an optionally substituted 2-substituted benzothiazolyl group.
  • a 2-substituted benzothiazolyl group has a group represented by —SR A0 at the 2-position.
  • R A0 is a hydrogen atom, a radically polymerizable group-containing group, or a cationically polymerizable group-containing group.
  • Both R A02 and R A03 are aromatic ring-containing groups having a radically polymerizable group-containing group, or both are aromatic ring-containing groups having a cationically polymerizable group-containing group.
  • the —NH— group attached to the triazine ring is attached to the aromatic rings in R A02 and R A03 .
  • a quinolinyl group which may have a substituent, an isoquinolinyl group which may have a substituent, and a 2-substituted benzothiazolyl group which may have a substituent all have high polarizability and a volume as a functional group. small. Therefore, R A01 is a quinolinyl group which may have a substituent, an isoquinolinyl group which may have a substituent, or a 2-substituted benzothiazolyl group which may have a substituent. It is believed that this contributes to the high refractive index of the cured product of the flexible composition.
  • the quinolinyl group as R A01 includes a quinolin-2-yl group, a quinolin-3-yl group, a quinolin-4-yl group, a quinolin-5-yl group, a quinolin-6-yl group, and a quinolin-7-yl group. , and quinolin-8-yl groups.
  • quinoline-3 is preferred because the starting compound for the compound represented by formula (A1) is easily available, and the compound represented by formula (A1) is easily synthesized.
  • -yl group and quinolin-4-yl group are preferred.
  • the isoquinolinyl group as R A01 includes isoquinolin-1-yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl, and isoquinolin-8-yl groups.
  • the quinolinyl group as R A01 and the substituent that the isoquinolinyl group may have are not particularly limited as long as the desired effect is not impaired.
  • substituents include halogen atoms, hydroxyl groups, mercapto groups, cyano groups, nitro groups, and monovalent organic groups.
  • a halogen atom as a substituent includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Monovalent organic groups include alkyl groups, alkoxy groups, alkoxyalkyl groups, aliphatic acyl groups, aliphatic acyloxy groups, alkoxycarbonyl groups, alkylthio groups, and aliphatic acylthio groups.
  • a radically polymerizable group-containing group and a cationically polymerizable group-containing group, which will be described later, are also preferred as the monovalent organic group.
  • the number of carbon atoms in the monovalent organic group as a substituent is not particularly limited as long as the desired effect is not impaired.
  • the number of carbon atoms in the monovalent organic group as a substituent is, for example, preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 8 or less.
  • the lower limit of the number of carbon atoms is 2.
  • alkyl groups as substituents include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include n-hexyl, n-heptyl, and n-octyl groups.
  • alkoxy groups as substituents include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n- Examples include pentyloxy, n-hexyloxy, n-heptyloxy, and n-octyloxy groups.
  • alkoxyalkyl groups as substituents include methoxymethyl group, ethoxymethyl group, n-propyloxymethyl group, n-butyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2- n-propyloxyethyl group, 2-n-butyloxyethyl group, 3-methoxy-n-propyloxy group, 3-ethoxy-n-propyloxy group, 3-n-propyloxy-n-propyloxy group, 3 -n-butyloxy-n-propyloxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, 4-n-propyloxy-n-butyloxy group, 4-n-butyloxy-n-butyloxy groups.
  • aliphatic acyl groups as substituents include acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, and octanoyl group.
  • aliphatic acyloxy groups as substituents include acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, and octanoyloxy groups.
  • alkoxycarbonyl groups as substituents include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl and sec-butyloxy. carbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, and n-octyloxycarbonyl groups.
  • alkylthio groups as substituents include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio and n-pentylthio. , n-hexylthio, n-heptylthio, and n-octylthio groups.
  • aliphatic acylthio groups as substituents include an acetylthio group, a propionylthio group, a butanoylthio group, a pentanoylthio group, a hexanoylthio group, a heptanoylthio group, and an octanoylthio group.
  • the number of substituents is not particularly limited as long as the desired effect is not impaired.
  • the number of substituents is preferably 1 or more and 4 or less, more preferably 1 or 2, and particularly preferably 1.
  • the quinolinyl group and the isoquinolinyl group have multiple substituents, the multiple substituents may be different from each other.
  • the 2-substituted benzothiazolyl group as R A01 has a group represented by —S—R A0 at the 2-position.
  • the 2-substituted benzothiazolyl group as R A01 may have a substituent other than the group represented by —S—R A0 at a position other than 2.
  • R A0 is a hydrogen atom, a radically polymerizable group-containing group, or a cationically polymerizable group-containing group.
  • a radically polymerizable group-containing group or a cationically polymerizable group-containing group will be described later.
  • Preferred examples of 2-substituted benzothiazolyl groups include the following groups.
  • the substituent that the 2-substituted benzothiazolyl group as R A01 may have is the same as the substituent that the quinolinyl group and isoquinolinyl group may have.
  • the number of substituents is not particularly limited as long as the desired effects are not impaired.
  • the number of substituents is preferably 1 or 2, more preferably 1.
  • the 2-substituted benzothiazolyl group has multiple substituents, the multiple substituents may be different from each other.
  • Both R A02 and R A03 are aromatic ring-containing groups having a radically polymerizable group-containing group, or both are aromatic ring-containing groups having a cationically polymerizable group-containing group.
  • the —NH— group attached to the triazine ring is attached to the aromatic rings in R A02 and R A03 .
  • the bonding position of the radically polymerizable group-containing group or the cationically polymerizable group-containing group in the aromatic ring-containing group as R A02 and R A03 is not particularly limited.
  • the number of radically polymerizable group-containing groups or cationically polymerizable group-containing groups in the aromatic ring-containing group as RA02 , and the number of radically polymerizable group-containing groups or cationically polymerizable group-containing groups in the aromatic ring-containing group as RA03 is not particularly limited.
  • the number of radically polymerizable group-containing groups or cationically polymerizable group-containing groups in the aromatic ring-containing group as RA02 , and the number of radically polymerizable group-containing groups or cationically polymerizable group-containing groups in the aromatic ring-containing group as RA03 The number of is preferably an integer of 1 or more and 3 or less, more preferably 1 or 2, and particularly preferably 1.
  • the aromatic ring-containing groups as R A02 and R A03 may contain only one monocyclic aromatic ring or one condensed aromatic ring, and the monocyclic aromatic ring and/or condensed aromatic ring may include two or more.
  • the aromatic ring-containing group as R A02 and R A03 contains two or more monocyclic aromatic rings and/or condensed aromatic rings, the monocyclic aromatic rings, the condensed aromatic rings, or the monocyclic
  • the type of linking group that links the formula aromatic ring and the condensed aromatic ring is not particularly limited.
  • the linking group may be a divalent linking group or a trivalent or higher linking group, preferably a divalent linking group.
  • a group represented by —CR a001 R a002 — is also preferred as the divalent linking group.
  • R a001 and R a002 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogenated alkyl group having 1 to 4 carbon atoms.
  • R a001 and R a002 may combine with each other to form a ring.
  • Specific examples of the group represented by —CR a001 R a002 — include methylene group, ethane-1,1-diyl group, propane-2,2-diyl group, butane-2,2-diyl group, 1,1 , 1,3,3,3-hexafluoropropane-2,2-diyl, cyclopentylidene, cyclohexylidene, and cycloheptylidene groups.
  • the aromatic ring-containing group as R A02 and R A03 has a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
  • the radically polymerizable group-containing group and the cationically polymerizable group-containing group are as described above.
  • Preferable examples of the radically polymerizable group-containing group include groups represented by the following formula (AI) or the following formula (A-II), which are not vinyloxy group-containing groups. -(A 01 ) na -R 01 (AI) -(A 01 ) na -R 02 -A 02 -R 01 (A-II)
  • R 01 is an alkenyl group having 2 to 10 carbon atoms.
  • R 02 is an alkylene group having 1 to 10 carbon atoms.
  • a 01 is -O-, -S-, -CO-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -CO-NH-, -NH-CO -, or -NH-.
  • a 02 is -O-, -S-, -CO-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -CO-NH-, -NH-CO -, or -NH-.
  • na is 0 or 1;
  • the radically polymerizable group-containing group include: —OR 03 , -SR 03 , —O—CH 2 CH 2 —OR 03 , —O—CH 2 CH 2 CH 2 —OR 03 , —O—CH 2 CH 2 CH 2 CH 2 —OR 03 , —CO—O—CH 2 CH 2 —OR 03 , —CO—O—CH 2 CH 2 CH 2 —OR 03 , —CO—O—CH 2 CH 2 CH 2 CH 2 —OR 03 , -O - CH2CH2 - NH-R03, -O - CH2CH2CH2 - NH- R03 , -O - CH2CH2CH2CH2 - NH - R03 , -CO-O - CH2CH2 - NH-R03, -CO-O - CH2CH2 - NH-R03, -CO-O - CH2CH2 - NH-R03, -CO-O - CH2CH
  • Suitable examples of the cationically polymerizable group-containing group include vinyloxy groups and groups represented by the following formulas (A3) to (A8). -(A 01 ) na -R 04 (A3) -(A 01 ) na -R 02 -R 05 (A4) -(A 01 ) na -R 02 -(CO) nb -A 03 -R 04 (A5) -(A 01 ) na -R 02 -(CO) nb -A 03 -R 07 -R 05 (A6) -(A 01 ) na -R 02 -OR 06 (A7) —(A 01 ) na —R 02 —(CO) nb —A 03 —R 07 —OR 06 (A8)
  • R 02 is an alkylene group having 1 to 10 carbon atoms.
  • R 04 is an epoxyalkyl group having 2 to 20 carbon atoms or an alicyclic epoxy group having 3 to 20 carbon atoms.
  • R 05 is an alicyclic epoxy group having 3 to 20 carbon atoms.
  • R 06 is a vinyl group.
  • R 07 is an alkylene group having 1 to 10 carbon atoms.
  • a 01 is -O-, -S-, -CO-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -CO-NH-, -NH-CO -, or -NH-.
  • a 03 is -O- or -NH-.
  • nb is 0 or 1;
  • Suitable specific examples of the cationically polymerizable group-containing group include: -R 08 , -O - CH2CH2 - R08, -O - CH2CH2CH2 - R08 , -O - CH2CH2CH2CH2 - R08 , -CO-O - CH2CH2 - R08, -CO-O - CH2CH2CH2 - R08 , -CO - O - CH2CH2CH2CH2 - R08 , -NH - CH2CH2 - R08, -NH - CH2CH2CH2 - R08 , -NH - CH2CH2CH2CH2 - R08 , -CO-NH - CH2CH2 - R08, —CO—NH—CH 2 CH 2 CH 2 —R 08 , and A group represented by —CO—NH—CH 2 CH 2 CH 2 CH 2 —R 08 can be mentioned.
  • R 08 in these groups is a vinyloxy group, a glycidyloxy group, a glycidylthio group, an epoxycyclopentyl group, an epoxycyclohexyl group, or an epoxycycloheptyl group.
  • R A02 and R A03 When the aromatic ring-containing group as R A02 and R A03 has one radically polymerizable group-containing group or cationically polymerizable group-containing group, suitable examples of R A02 and R A03 are groups of the following formula are mentioned.
  • PG is a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
  • X A is selected from the group consisting of a (meth)acryloyloxy group, a (meth)acryloylthio group, a 3-(meth)acryloyloxy-2-hydroxy-n-propyloxycarbonyl group, and a glycidyloxy group. It is a group that is
  • the method for producing the compound represented by formula (A-1a) is not particularly limited. Typically, it can be produced by reacting a cyanuric halide such as cyanuric chloride with an aromatic amine represented by R A01 —NH 2 , R A02 —NH 2 and R A03 —NH 2 . These plural kinds of amines may be reacted with cyanuric halide simultaneously or sequentially with cyanuric halide, and it is preferable to react with cyanuric halide sequentially.
  • a cyanuric halide such as cyanuric chloride
  • aromatic amine represented by R A01 —NH 2 , R A02 —NH 2 and R A03 —NH 2 aromatic amine represented by R A01 —NH 2 , R A02 —NH 2 and R A03 —NH 2 .
  • R A02 and R A03 in the formula (A1) are, after reacting an aromatic amine having a functional group such as a hydroxyl group, a mercapto group, a carboxy group, or an amino group, with a cyanuric halide, these functional groups. It can also be produced by reacting a radically polymerizable group-containing group or a compound that provides a cationic polymerizable group-containing group.
  • Compounds that provide radically polymerizable group-containing groups and cationically polymerizable group-containing groups include polymerization of (meth)acrylic acid, (meth)acrylic acid halides, halogenated olefins, epichlorohydrin, glycidyl (meth)acrylate, and the like. compounds having a functional group.
  • a functional group such as a hydroxyl group, a mercapto group, a carboxyl group, or an amino group and a compound having a polymerizable group
  • an ether bond, a carboxylic acid ester bond, a carboxylic acid amide bond, and a thioether bond are generated. reactions can be employed.
  • the reaction for forming the radically polymerizable group-containing group or the cationically polymerizable group-containing group may be a multistage reaction. For example, after reacting a cyanuric halide with an aromatic amine having a phenolic hydroxyl group, the phenolic hydroxyl group is reacted with epichlorohydrin to form a glycidyl group, and then the glycidyl group is reacted with acrylic acid to give the following formula: A radically polymerizable group-containing group represented by can be introduced onto the aromatic ring.
  • the compound represented by formula (A-1a) is usually synthesized in an organic solvent.
  • an organic solvent is not particularly limited as long as it is an inert solvent that does not react with cyanuric halides, aromatic amines, radically polymerizable groups, cationic polymerizable groups, and the like.
  • an organic solvent or the like exemplified as a specific example of the solvent (S) can be used.
  • cyanuric halide and aromatic amines represented by R A01 —NH 2 , R A02 —NH 2 , and R A03 —NH 2 The temperature at which the group amines are reacted is not particularly limited. Typically, the reaction temperature is preferably from 0°C to 150°C.
  • Another preferred example of the compound represented by formula (A-1) is a compound represented by formula (A-1b) below.
  • R A11 , R A12 and R A13 each represent an aromatic ring-containing group. At least one of R A12 and R A13 is a group represented by the following formula (A-1b-1). The -NH- groups attached to the triazine ring are attached to the aromatic rings in R A11 , R A12 and R A13 respectively.
  • R a11 and R a12 are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
  • nA1 and nA2 are each independently an integer of 0 or more and 4 or less.
  • R a13 and R a14 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a phenyl group. R a13 and R a14 may combine with each other to form a ring.
  • RA14 is a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
  • R A12 and R A13 are groups represented by formula (A-1b-1)
  • R A12 and R A13 both have a radically polymerizable group-containing group, or both have a cationically polymerizable group It has a containing group.
  • R A11 , R A12 and R A13 are each aromatic ring-containing groups.
  • the —NH— groups attached to the triazine ring are attached to the aromatic rings in R A11 , R A12 and R A13 , respectively.
  • the aromatic ring-containing group is a group other than the group represented by formula (A-1b-1)
  • the aromatic ring-containing group is not particularly limited as long as it satisfies the given requirements above.
  • Aromatic ring-containing groups other than the group represented by formula (A-1b-1) may contain only one monocyclic aromatic ring, or one condensed aromatic ring, monocyclic aromatic ring, and/or may contain two or more fused aromatic rings.
  • the aromatic ring-containing group contains two or more monocyclic aromatic rings and/or condensed aromatic rings, the monocyclic aromatic rings together, the condensed aromatic rings together, or the monocyclic aromatic ring and the condensed aromatic ring
  • the type of the linking group that links the is not particularly limited.
  • the linking group may be a divalent linking group or a trivalent or higher linking group, preferably a divalent linking group.
  • Preferred examples of the aromatic ring-containing group include optionally substituted quinolinyl groups, optionally substituted isoquinolinyl groups, and optionally substituted 2-substituted benzothiazolyl groups. These groups include an optionally substituted quinolinyl group, an optionally substituted isoquinolinyl group, and an optionally substituted quinolinyl group, which are described with respect to R A01 in formula (A-1a). It is the same as the 2-substituted benzothiazolyl group.
  • aromatic ring-containing group examples include an optionally substituted phenyl group, an optionally substituted naphthyl group, an optionally substituted biphenylyl group, and an optionally substituted phenyl group.
  • optionally substituted phenylthiophenyl group optionally substituted phenoxyphenyl group, optionally substituted phenylsulfonylphenyl group, optionally substituted benzothiazolyl group, optionally substituted a benzoxazolyl group which may be substituted, a terphenyl group which may have a substituent, and the like.
  • substituents are the same as the substituents that the quinolinyl group and the isoquinolinyl group may have.
  • these groups have multiple substituents the multiple substituents may be different from each other.
  • Suitable specific examples of the naphthyl group which may have a substituent include naphthalene-1-yl group and naphthalene-2-yl group.
  • biphenylyl group optionally having a substituent include a 4-phenylphenyl group, a 3-phenylphenyl group, a 2-phenylphenyl group, a 4-(4-nitrophenyl)phenyl group, a 3-(4 -nitrophenyl)phenyl, 2-(4-nitrophenyl)phenyl, 4-(4-cyanophenyl)phenyl, 3-(4-cyanophenyl)phenyl, and 2-(4-cyanophenyl)phenyl groups.
  • phenylsulfonylphenyl group which may have a substituent include a 4-phenylsulfonylphenyl group, a 3-phenylsulfonylphenyl group, and a 2-phenylsulfonylphenyl group.
  • the aromatic ring-containing group other than the group represented by formula (A-1b-1) may have a radically polymerizable group-containing group or a cationically polymerizable group-containing group as a substituent.
  • the bonding position of the radically polymerizable group-containing group or the cationically polymerizable group-containing group in the aromatic ring-containing group is not particularly limited.
  • the number of radically polymerizable group-containing groups or cationically polymerizable group-containing groups in the aromatic ring-containing group is not particularly limited.
  • the number of radical polymerizable group-containing groups or cationically polymerizable group-containing groups in the aromatic ring-containing group is preferably an integer of 1 or more and 3 or less, more preferably 1 or 2, and particularly preferably 1.
  • aromatic ring-containing group has one radically polymerizable group-containing group or one cationically polymerizable group-containing group
  • suitable examples of such groups include groups of the following formulae.
  • PG is a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
  • R A12 and R A13 has the following formula (A-1b-1): It is a group represented by In formula (A-1b-1), R a11 and R a12 are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. nA1 and nA2 are each independently an integer of 0 or more and 4 or less. R a13 and R a14 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a phenyl group.
  • R a13 and R a14 may combine with each other to form a ring.
  • RA14 is a radically polymerizable group-containing group or a cationically polymerizable group-containing group.
  • R A12 and R A13 are groups represented by formula (A-1b-1)
  • R A12 and R A13 both have a radically polymerizable group-containing group, or both have a cationically polymerizable group It has a containing group.
  • alkyl groups having 1 to 4 carbon atoms as R a11 and R a12 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert -Butyl group.
  • the alkoxy group having 1 to 4 carbon atoms as R a11 and R a12 includes a methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group and sec-butyloxy group. , and tert-butyloxy groups.
  • Halogen atoms as R a11 and R a12 include fluorine, chlorine, bromine and iodine atoms.
  • alkyl group having 1 to 4 carbon atoms for R a13 and R a14 are the same as the specific examples of the alkyl group having 1 to 4 carbon atoms for R a11 and R a12 .
  • halogenated alkyl groups having 1 to 4 carbon atoms for R a13 and R a14 include chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 3,3,3-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group and the like.
  • Preferred examples of the group represented by formula (A-1b-1) include groups represented by the following formula.
  • the group represented by formula (A-1b-1) has a radically polymerizable group-containing group or a cationically polymerizable group-containing group as R A14 .
  • the radically polymerizable group-containing group and the cationically polymerizable group-containing group are as described above.
  • Preferred specific examples of the radically polymerizable group-containing group and preferred specific examples of the cationically polymerizable group-containing group are the preferred radically polymerizable group-containing groups described for the compound represented by formula (A1-a).
  • Specific examples and preferred specific examples of the cationically polymerizable group-containing group are the same.
  • X A is selected from the group consisting of a (meth)acryloyloxy group, a (meth)acryloylthio group, a 3-(meth)acryloyloxy-2-hydroxy-n-propyloxycarbonyl group, and a glycidyloxy group.
  • Y A is a quinolin-3-yl group, phenyl group, 4-cyanophenyl group, 3-cyanophenyl group, 2-cyanophenyl group, 3,4-dicyanophenyl group, 4-nitrophenyl group, 4-methoxyphenyl group, 4-phenylthiophenyl group, 4-phenylsulfonylphenyl group, 4-iodophenyl group, benzothiazol-2-yl group, 2-mercaptobenzothiazol-5-yl group, 4-phenylphenyl group, 4-( 4-nitrophenyl)phenyl group, 4-(4-cyanophenyl)phenyl group, naphthalen-1-yl group, and 4-(4-phenylphenyl)phenyl group.
  • the method for producing the compound represented by formula (A-1b) is not particularly limited. Typically, it can be produced by reacting a cyanuric halide such as cyanuric chloride with an aromatic amine represented by R A11 —NH 2 , R A12 —NH 2 and R A13 —NH 2 . These plural kinds of amines may be reacted with cyanuric halide simultaneously or sequentially with cyanuric halide, and it is preferable to react with cyanuric halide sequentially.
  • a cyanuric halide such as cyanuric chloride
  • an aromatic amine represented by R A11 —NH 2 , R A12 —NH 2 and R A13 —NH 2 aromatic amine represented by R A11 —NH 2 , R A12 —NH 2 and R A13 —NH 2 .
  • the aromatic ring-containing group bonded to the triazine ring via -NH- has a radically polymerizable group-containing group or a cationically polymerizable-containing group
  • a functional group such as a hydroxyl group, a mercapto group, a carboxyl group, or an amino group
  • these functional groups are also radically polymerizable group-containing groups by reacting a compound that provides a radically polymerizable group-containing group or a cationically polymerizable group-containing group. , or cationically polymerizable containing groups.
  • Compounds that provide radically polymerizable group-containing groups and cationically polymerizable group-containing groups include polymerization of (meth)acrylic acid, (meth)acrylic acid halides, halogenated olefins, epichlorohydrin, glycidyl (meth)acrylate, and the like. compounds having a functional group.
  • a functional group such as a hydroxyl group, a mercapto group, a carboxyl group, or an amino group and a compound having a polymerizable group
  • an ether bond, a carboxylic acid ester bond, a carboxylic acid amide bond, and a thioether bond are generated. reactions can be employed.
  • the reaction for forming the radically polymerizable group-containing group or the cationically polymerizable group-containing group may be a multistage reaction. For example, after reacting a cyanuric halide with an aromatic amine having a phenolic hydroxyl group, the phenolic hydroxyl group is reacted with epichlorohydrin to glycidylate, and then the glycidyl group is reacted with acrylic acid to obtain the following formula.
  • a radically polymerizable group-containing group represented by can be introduced onto the aromatic ring.
  • the compound represented by formula (A-1b) is usually synthesized in an organic solvent.
  • an organic solvent is not particularly limited as long as it is an inert solvent that does not react with cyanuric halides, aromatic amines, radically polymerizable groups, cationic polymerizable groups, and the like.
  • an organic solvent or the like exemplified as a specific example of the solvent (S) can be used.
  • cyanuric halide and aromatic amines represented by R A11 —NH 2 , R A12 —NH 2 , and R A13 —NH 2 The temperature at which the group amines are reacted is not particularly limited. Typically, the reaction temperature is preferably from 0°C to 150°C.
  • the content of the photopolymerizable compound (A) in the photocurable composition is not particularly limited as long as the desired effects are not impaired.
  • the content of the photopolymerizable compound (A) in the photocurable composition is 0.1 parts by mass when the mass of the photocurable composition excluding the mass of the solvent (S) described later is 100 parts by mass. 50 parts by mass or less is preferable, 0.5 parts by mass or more and 40 parts by mass or less is more preferable, and 1 part by mass or more and 25 parts by mass or less is particularly preferable.
  • the photocurable composition contains metal oxide fine particles (B).
  • the type of metal oxide that constitutes the metal oxide fine particles (B) is not particularly limited as long as the desired effects are not impaired.
  • Preferred examples of the metal oxide fine particles (B) include at least one selected from the group consisting of zirconium oxide fine particles, titanium oxide fine particles, barium titanate fine particles, and cerium oxide fine particles.
  • the photocurable composition may contain one type of these metal oxide fine particles (B) alone, or may contain two or more types in combination. When the photocurable composition contains the metal oxide fine particles (B), it is possible to form a cured product exhibiting a high refractive index.
  • the average particle size of the metal oxide fine particles (B) is preferably 500 nm or less, preferably 2 nm or more and 100 nm or less, from the viewpoint of the transparency of the cured product.
  • the surface of the metal oxide fine particles (B) is preferably modified with an ethylenically unsaturated double bond-containing group.
  • the photopolymerizable compound (A) is added together with the metal oxide fine particles (B) when forming a cured product. While polymerizing, the metal oxide nanoparticles (B) are fixed in the matrix consisting of the polymer of the photopolymerizable compound (A). Since this makes it difficult for the metal oxide fine particles (B) to aggregate, when the surface of the metal oxide fine particles (B) is modified with an ethylenically unsaturated double bond-containing group It is particularly easy to suppress the localization of (B).
  • metal oxide fine particles (B) For example, by allowing a capping agent containing an ethylenically unsaturated double bond to act on the surface of the metal oxide fine particles (B), the surface of the metal oxide fine particle (B) is exposed to an ethylenically unsaturated double bond through a chemical bond such as a covalent bond. Metal oxide fine particles (B) modified with containing groups are obtained.
  • the method of bonding the capping agent containing an ethylenically unsaturated double bond to the surface of the metal oxide fine particles (B) via a chemical bond such as a covalent bond is not particularly limited. Hydroxyl groups are usually present on the surface of the metal oxide fine particles (B). By reacting the hydroxyl group with the reactive group of the capping agent, the capping agent is covalently bonded to the surface of the metal oxide fine particles (B).
  • a trialkoxysilyl group such as a trimethoxysilyl group and a triethoxysilyl group
  • a dialkoxysilyl group such as a dimethoxysilyl group and a diethoxysilyl group
  • a trialkoxysilyl group, a dialkoxysilyl group, a monoalkoxysilyl group, a trihalosilyl group, a dihalosilyl group, and a monohalosilyl group form a siloxane bond with the surface of the metal oxide nanoparticles (B).
  • a carboxy group and a halocarbonyl group form a bond represented by (metal oxide —O—CO—) with the surface of the metal oxide nanoparticles (B).
  • a hydroxyl group forms a bond represented by (metal oxide —O—) with the surface of the metal oxide fine particles (B).
  • the groups that bind to the above reactive groups include hydrogen atoms and various organic groups.
  • the organic group may contain heteroatoms such as O, N, S, P, B, Si, and halogen atoms.
  • the groups that bind to the above reactive groups include, for example, linear or branched alkyl groups that may be interrupted by oxygen atoms (—O—), linear or branched an alkenyl group optionally interrupted by an oxygen atom (--O--), may be linear or branched, and is interrupted by an oxygen atom (--O--) alkynyl groups, cycloalkyl groups, aromatic hydrocarbon groups, heterocyclic groups, etc., which may be substituted.
  • substituents such as halogen atoms, epoxy group-containing groups such as glycidyl groups, hydroxyl groups, mercapto groups, amino groups, (meth)acryloyl groups, and isocyanate groups.
  • substituents such as halogen atoms, epoxy group-containing groups such as glycidyl groups, hydroxyl groups, mercapto groups, amino groups, (meth)acryloyl groups, and isocyanate groups.
  • the number of substituents is not particularly limited.
  • R b1 , R b2 , R b3 and Rb4 are each an organic group which may be the same or different.
  • organic groups include alkyl groups such as methyl group and ethyl group; alkenyl groups such as vinyl group and allyl group; aromatic hydrocarbon groups such as phenyl group, naphthyl group and tolyl group; Epoxy group-containing groups such as propyl group; (meth)acryloyloxy group and the like.
  • r and s in the above formula are each independently an integer of 0 or more and 60 or less. Both r and s in the above formula cannot be zero.
  • capping agents include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 1-hexenyltrimethoxysilane, 1-hexenyltriethoxysilane, 1-octenyltrimethoxysilane. Unsaturated groups such as silane, 1-octenyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloylpropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, etc.
  • alkoxysilane Containing alkoxysilane; unsaturated group-containing alcohols such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, allyl alcohol, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, and 3-allyloxypropanol (meth)acrylic acid; (meth)acrylic acid halides such as (meth)acrylic acid chloride;
  • the amount of the capping agent used when bonding the capping agent to the surface of the metal oxide fine particles (B) via a chemical bond such as a covalent bond is not particularly limited.
  • a sufficient amount of the capping agent is used to react with almost all hydroxyl groups on the surface of the metal oxide fine particles (B).
  • the content of the metal oxide fine particles (B) in the photocurable composition is not particularly limited as long as the object of the present invention is not impaired.
  • the content of the metal oxide nanoparticles (B) in the photocurable composition is preferably 5% by mass or more and 95% by mass or less with respect to the mass of the photocurable composition excluding the mass of the solvent (S). , more preferably 35% by mass or more and 93% by mass or less, and even more preferably 40% by mass or more and 90% by mass or less.
  • the content of the metal oxide fine particles (B) in the photocurable composition is within the above range, the localization of the metal oxide fine particles (B) in the cured product is suppressed, and high refractive index curing is achieved. Easy to form things.
  • the content of the metal oxide fine particles (B) in the photocurable composition is the mass excluding the mass of the solvent (S) in the photocurable composition. is preferably 70% by mass or more, more preferably 70% by mass or more and 95% by mass or less, and even more preferably 70% by mass or more and 90% by mass or less.
  • the lower limit of the content of the metal oxide fine particles (B) in the photocurable composition may be 65% by mass or more.
  • the surface of the metal oxide fine particles (B) is modified with an ethylenically unsaturated double bond-containing group
  • the ethylenically unsaturated double bond-containing groups present on the surface of the metal oxide fine particles (B) is included in the mass of the metal oxide fine particles (B).
  • the photocurable composition contains an initiator (C).
  • a radical polymerization initiator (C1) is used as the initiator (C).
  • a cationic polymerization initiator (C2) is used as the initiator (C).
  • the initiator (C) light is used as the initiator (C) because it is possible to perform site-selective curing of the photocurable composition and there is no concern about deterioration, volatilization, sublimation, etc. of the components of the photocurable composition due to heat.
  • An initiator is used.
  • the initiator (C) is not particularly limited, and conventionally known various polymerization initiators can be used.
  • Photoradical polymerization initiators useful as the radical polymerization initiator (C1) include, specifically, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[ 4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1 -(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2- methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, O- Acetyl-1-[6-(2-methylbenzoyl)-9-ethy
  • oxime ester compounds are preferred from the viewpoint of the sensitivity of the photocurable composition.
  • a compound having a partial structure represented by the following formula (c1) is preferable.
  • n1 is 0 or 1
  • R c2 is a monovalent organic group
  • R c3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group
  • * is a bond.
  • the compound having the partial structure represented by formula (c1) preferably has a carbazole skeleton, fluorene skeleton, diphenyl ether skeleton, or phenyl sulfide skeleton.
  • the compound having the partial structure represented by formula (c1) preferably has one or two partial structures represented by formula (c1).
  • Compounds having a partial structure represented by formula (c1) include compounds represented by the following formula (c2).
  • R c1 is a group represented by the following formula (c3), (c4), or (c5), n1 is 0 or 1, R c2 is a monovalent organic group, R c3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group.
  • R c4 and R c5 are each independently a monovalent organic group, n2 is an integer of 0 or more and 3 or less, When n2 is 2 or 3, multiple R c5 may be the same or different, and multiple R c5 may combine with each other to form a ring. * is a bond.
  • R c6 and R c7 each independently represent an optionally substituted chain alkyl group, an optionally substituted chain alkoxy group, a substituted is a cyclic organic group or a hydrogen atom, R c6 and R c7 may combine with each other to form a ring, R c7 and the benzene ring in the fluorene skeleton may be bonded to each other to form a ring, R c8 is a nitro group or a monovalent organic group, n3 is an integer of 0 to 4, * is a bond.
  • R c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group, A is S or O; n4 is an integer of 0 to 4, * is a bond.
  • R c4 is a monovalent organic group.
  • R c4 can be selected from various organic groups as long as the objects of the present invention are not impaired.
  • a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. is more preferred.
  • the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
  • R c4 include an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, and a carbon atom
  • a saturated aliphatic acyl group optionally having 2 to 20 substituents, an alkoxycarbonyl group having 2 to 20 carbon atoms optionally having a substituent, a phenyl group optionally having a substituent , an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted phenylalkyl group having 7 to 20 carbon atoms, having a substituent optionally substituted naphthyl group, optionally substituted naphthoxycarbonyl group, optionally substituted naphthylalkyl group having 11 to 20 carbon atoms, substituted a heterocyclyl group optionally having a group, a heterocyclylcarbonyl group optionally having a substituent, and the like.
  • an alkyl group having 1 to 20 carbon atoms is preferable.
  • the alkyl group may be linear or branched.
  • the number of carbon atoms in the alkyl group as R c4 is preferably 2 or more, more preferably 5 or more, from the viewpoint of good solubility in the photocurable composition of the compound represented by formula (c3). 7 or more is particularly preferred.
  • the number of carbon atoms in the alkyl group as R c4 is 15. The following is preferable, and 10 or less is more preferable.
  • R c4 has a substituent
  • substituents include a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 2 to 20 carbon atoms.
  • the heterocyclyl group may be an aliphatic heterocyclic group or an aromatic heterocyclic group.
  • the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more of N, S, O, or such monocyclic rings are fused together or such monocyclic ring is fused with a benzene ring. is a heterocyclyl group.
  • the heterocyclyl group is a condensed ring, it has up to 3 rings.
  • Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; be done.
  • R c4 is a heterocyclyl group
  • substituents that the heterocyclyl group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, and the like.
  • R c4 examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include isopentyl, neopentyl, pentan-3-yl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl groups.
  • n-octyl group and 2-ethylhexyl group are preferred, and 2-ethylhexyl group is more preferred, from the viewpoint of good solubility of the compound represented by formula (c3) in the photocurable composition.
  • R c5 is a monovalent organic group.
  • R c5 can be selected from various organic groups as long as the objects of the present invention are not impaired.
  • a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. is more preferred.
  • the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
  • Examples of monovalent organic groups suitable as R c5 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, and substituents.
  • optionally substituted phenyl group optionally substituted phenoxy group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally substituted benzoyloxy a phenylalkyl group optionally having substituents, a naphthyl group optionally having substituents, a naphthoxy group optionally having substituents, a naphthoyl group optionally having substituents, a substituent an optionally substituted naphthoxycarbonyl group, an optionally substituted naphthyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, an optionally substituted heterocyclylcarbonyl group, amino group substituted with one or two organic groups, morpholin-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group, HX 2 C- or H 2 Substituents including a group represented by XC— (where each X is
  • R c5 is an alkyl group
  • the number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less.
  • R c5 is an alkyl group, it may be linear or branched. Specific examples of R c5 being an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and n-pentyl groups.
  • R c5 is an alkyl group
  • the alkyl group may contain an ether bond (--O--) in the carbon chain.
  • alkyl groups having an ether bond in the carbon chain examples include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.
  • R c5 is an alkoxy group
  • the number of carbon atoms in the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less.
  • R c5 is an alkoxy group, it may be linear or branched.
  • R c5 being an alkoxy group
  • R c5 being an alkoxy group
  • R c5 being an alkoxy group
  • R c5 being an alkoxy group
  • R c5 isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group , tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, and isodecyloxy group.
  • R c5 is an alkoxy group
  • the alkoxy group may contain an ether bond (--O--) in the carbon chain.
  • alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, methoxypropyloxy and the like.
  • R c5 is a cycloalkyl group or a cycloalkoxy group
  • the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less.
  • Specific examples of R c5 being a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • R c5 being a cycloalkoxy group
  • R c5 being a cycloalkoxy group
  • R c5 being a cycloalkoxy group
  • R c5 being a cycloalkoxy group
  • R c5 being a cycloalkoxy group
  • R c5 being a cycloalkoxy group
  • R c5 is a saturated aliphatic acyl group or saturated aliphatic acyloxy group
  • the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 or more and 21 or less, more preferably 2 or more and 7 or less.
  • R c5 being a saturated aliphatic acyl group
  • R c5 being a saturated aliphatic acyl group
  • R c5 being a saturated aliphatic acyl group
  • R c5 being a saturated aliphatic acyl group
  • R c5 being a saturated aliphatic acyl group
  • R c5 being a saturated aliphatic acyl group
  • R c5 being a saturated aliphatic acyl group
  • R c5 being a saturated aliphatic acyl group
  • R c5 being a saturated aliphatic acyl group
  • R c5 being a saturated aliphatic acyloxy group
  • R c5 being a saturated aliphatic acyloxy group
  • R c5 being a saturated aliphatic acyloxy group
  • R c5 being a saturated aliphatic acyloxy group
  • R c5 being a saturated aliphatic acyloxy group
  • R c5 is an alkoxycarbonyl group
  • the number of carbon atoms in the alkoxycarbonyl group is preferably 2 or more and 20 or less, more preferably 2 or more and 7 or less.
  • Specific examples of R c5 being an alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, sec-butyl oxycarbonyl group, tert-butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbony
  • R c5 is a phenylalkyl group
  • the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less.
  • R c5 is a naphthylalkyl group
  • the number of carbon atoms in the naphthylalkyl group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less.
  • Specific examples of R c5 being a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group and a 4-phenylbutyl group.
  • R c5 being a naphthylalkyl group
  • R c5 being a naphthylalkyl group
  • R c5 may further have a substituent on the phenyl group or naphthyl group.
  • R c5 is a heterocyclyl group
  • the heterocyclyl group is the same as when R c4 in formula (c3) is a heterocyclyl group, and the heterocyclyl group may further have a substituent.
  • R c5 is a heterocyclylcarbonyl group
  • the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as when R c5 is a heterocyclyl group.
  • R c5 is an amino group substituted with 1 or 2 organic groups
  • preferred examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, saturated aliphatic acyl group having 2 to 21 carbon atoms, optionally substituted phenyl group, optionally substituted benzoyl group, optionally substituted 7 to 20 carbon atoms
  • amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n- butylamino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino
  • the substituent includes a group represented by HX 2 C-- or H 2 XC-- (eg, HX 2 C— or H 2 XC—, a halogenated alkoxy group containing a group represented by HX 2 C— or H 2 XC—, a halogenated alkyl group containing a group represented by HX 2 C— or H 2 XC—), Alkyl group, alkoxy group having 1 to 6 carbon atoms, saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated fat having 2 to 7 carbon atoms group acyloxy group, monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl group,
  • the number of substituents is not limited as long as the object of the present invention is not impaired, and is preferably 1 to 4.
  • the phenyl group, naphthyl group and heterocyclyl group contained in R c5 have multiple substituents, the multiple substituents may be the same or different.
  • Substituents contained in R c5 when the benzoyl group further has a substituent include an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a 2-thenoyl group. (thiophen-2-ylcarbonyl group), furan-3-ylcarbonyl group and phenyl group.
  • the halogen atom represented by X includes a fluorine atom, a chlorine atom, a bromine atom, etc., and is preferably a fluorine atom.
  • the substituent containing a group represented by HX 2 C-- or H 2 XC-- includes a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC--, HX 2 C-- or H 2 XC- A group having a halogenated alkoxy group including a group represented by -, a halogenated alkyl group including a group represented by HX 2 C- or H 2 XC-, represented by HX 2 C- or H 2 XC- and a group having a halogenated alkyl group containing a group, such as a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC--, or represented by HX 2 C-- or H 2 XC-- More preferably, it is a group having a halogenated alkoxy group containing group.
  • the group having a halogenated alkyl group containing a group represented by HX 2 C-- or H 2 XC-- is substituted with a halogenated alkyl group containing a group represented by HX 2 C-- or H 2 XC--.
  • aromatic groups eg, phenyl group, naphthyl group, etc.
  • cycloalkyl groups substituted with halogenated alkyl groups including groups represented by HX 2 C-- or H 2 XC-- eg, cyclopentyl group, cyclohexyl groups, etc.
  • the group having a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC-- is substituted with a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC--.
  • aromatic groups e.g., phenyl group, naphthyl group, etc.
  • alkyl groups substituted with halogenated alkoxy groups including groups represented by HX 2 C- or H 2 XC- e.g., methyl group, ethyl group , n-propyl group, i-propyl group, etc.
  • a cycloalkyl group substituted with a halogenated alkoxy group including a group represented by HX 2 C- or H 2 XC- e.g., cyclopentyl group, cyclohexyl group, etc.
  • Rc5 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, and a phenylthioalkyl group optionally having a substituent on the aromatic ring.
  • the substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are the same as the substituents that the phenyl group contained in R c5 may have.
  • R c5 is an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, a cycloalkylalkyl group, or an aromatic ring which may have a substituent.
  • Good phenylthioalkyl groups are preferred.
  • the alkyl group an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. preferable.
  • the optionally substituted phenyl groups a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred.
  • the number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 or more and 10 or less, more preferably 5 or more and 8 or less, and particularly preferably 5 or 6.
  • the number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2.
  • a cyclopentylethyl group is preferred.
  • the number of carbon atoms in the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 or more and 8 or less, more preferably 1 or more and 4 or less, and particularly preferably 2.
  • a 2-(4-chlorophenylthio)ethyl group is preferred.
  • the formed ring when a plurality of R c5 are present and the plurality of R c5 are bonded to each other to form a ring, the formed ring includes a hydrocarbon ring, a heterocyclic ring, and the like. be done. Heteroatoms contained in heterocycles include, for example, N, O and S. Aromatic rings are particularly preferred as the ring formed by combining a plurality of R c5 s. Such an aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. As such an aromatic ring, an aromatic hydrocarbon ring is preferred. Specific examples of the case where a plurality of R c5 in formula (c3) are bonded to each other to form a benzene ring are shown below.
  • R c8 is a nitro group or a monovalent organic group.
  • R c8 is bonded to a 6-membered aromatic ring different from the aromatic ring bonded to the group represented by —(CO) n1 — on the condensed ring in formula (c4).
  • the bonding position of R c8 is not particularly limited.
  • the group represented by formula (c4) has one or more R c8 , one of the one or more R c8 is fluorene, because the compound represented by formula (c4) is easy to synthesize. Attachment to the 7-position of the backbone is preferred.
  • the group represented by formula (c4) when the group represented by formula (c4) has 1 or more R c8 , the group represented by formula (c4) is preferably represented by the following formula (c6). When there are multiple R c8s , the multiple R c8s may be the same or different.
  • R c6 , R c7 , R c8 and n3 are respectively the same as R c6 , R c7 , R c8 and n3 in formula (c4).
  • R c8 is not particularly limited as long as the object of the present invention is not impaired.
  • a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. is more preferred.
  • the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
  • Preferred examples of the monovalent organic group for R c8 include the same preferred examples of the monovalent organic group as R c5 in formula (c3).
  • R c6 and R c7 are each an optionally substituted chain alkyl group, an optionally substituted chain alkoxy group, an optionally substituted cyclic It is an organic group or a hydrogen atom. R c6 and R c7 may combine with each other to form a ring. Among these groups, chain alkyl groups which may have a substituent are preferable as R c6 and R c7 . When R c6 and R c7 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.
  • R c6 and R c7 are unsubstituted chain alkyl groups
  • the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly 1 or more and 6 or less.
  • Specific examples of R c6 and R c7 being chain alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group.
  • n-pentyl group isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, and isodecyl group.
  • R c6 and R c7 are alkyl groups
  • the alkyl group may contain an ether bond (--O--) in the carbon chain.
  • alkyl groups having an ether bond in the carbon chain examples include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.
  • R c6 and R c7 are chain alkyl groups having a substituent
  • the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less.
  • the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group.
  • a chain alkyl group having a substituent is preferably linear.
  • the substituents that the alkyl group may have are not particularly limited as long as they do not interfere with the object of the present invention. Suitable examples of substituents include alkoxy groups, cyano groups, halogen atoms, halogenated alkyl groups, cyclic organic groups, and alkoxycarbonyl groups.
  • Halogen atoms include fluorine, chlorine, bromine and iodine atoms. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferred.
  • Cyclic organic groups include cycloalkyl groups, aromatic hydrocarbon groups, and heterocyclyl groups. Specific examples of the cycloalkyl group are the same as the preferred examples when R c8 is a cycloalkyl group.
  • aromatic hydrocarbon groups include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl groups.
  • heterocyclyl group are the same as the preferred examples when R c8 is a heterocyclyl group.
  • R c8 is an alkoxycarbonyl group
  • the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, preferably linear.
  • the number of carbon atoms in the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.
  • the number of substituents is not particularly limited.
  • the preferred number of substituents varies depending on the number of carbon atoms in the chain alkyl group.
  • the number of substituents is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 6 or less.
  • R c6 and R c7 are chain alkoxy groups having no substituents
  • the number of carbon atoms in the chain alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly 1 or more and 6 or less. preferable.
  • R c6 and R c7 being chain alkoxy groups include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert -butyloxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like.
  • R c6 and R c7 are alkoxy groups
  • the alkoxy groups may contain an ether bond (--O--) in the carbon chain.
  • alkoxy groups having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propyloxyethoxyethoxy, methoxypropyloxy and the like.
  • R c6 and R c7 are chain alkoxy groups having substituents
  • the substituents that the alkoxy groups may have are the same as in the case where R c6 and R c7 are chain alkyl groups.
  • R c6 and R c7 are cyclic organic groups
  • the cyclic organic group may be an alicyclic group or an aromatic group.
  • Cyclic organic groups include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclyl groups.
  • R c6 and R c7 are cyclic organic groups, the substituents that the cyclic organic groups may have are the same as in the case where R c6 and R c7 are chain alkyl groups.
  • the aromatic hydrocarbon group is either a phenyl group or a group formed by combining multiple benzene rings via carbon-carbon bonds. , is preferably a group formed by condensing a plurality of benzene rings.
  • the aromatic hydrocarbon group is a phenyl group or a group formed by combining or condensing a plurality of benzene rings
  • the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, 3 or less is preferable, 2 or less is more preferable, and 1 is particularly preferable.
  • Preferred specific examples of aromatic hydrocarbon groups include phenyl, naphthyl, biphenylyl, anthryl, and phenanthryl groups.
  • R c6 and R c7 are aliphatic cyclic hydrocarbon groups
  • the aliphatic cyclic hydrocarbon groups may be monocyclic or polycyclic.
  • the number of carbon atoms in the aliphatic cyclic hydrocarbon group is not particularly limited, it is preferably 3 or more and 20 or less, more preferably 3 or more and 10 or less.
  • Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, A tetracyclododecyl group, an adamantyl group, and the like can be mentioned.
  • R c6 and R c7 are heterocyclyl groups
  • the same heterocyclyl groups as R c5 in formula (c3) can be mentioned.
  • R c6 and R c7 may combine with each other to form a ring.
  • a group consisting of a ring formed by R c6 and R c7 is preferably a cycloalkylidene group.
  • the ring constituting the cycloalkylidene group is preferably a 5- to 6-membered ring, more preferably a 5-membered ring.
  • the ring may be either an aromatic ring or an aliphatic ring.
  • the cycloalkylidene group may be fused with one or more other rings.
  • rings that may be condensed with a cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, and pyridine.
  • R c6 and R c7 examples include groups represented by the formula -A 1 -A 2 .
  • a 1 is a linear alkylene group
  • a 2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.
  • the number of carbon atoms in the linear alkylene group for A 1 is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.
  • A2 is an alkoxy group
  • the alkoxy group may be linear or branched, preferably linear.
  • the number of carbon atoms in the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.
  • A2 is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom.
  • the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom, a chlorine atom or a bromine atom.
  • the halogenated alkyl group may be linear or branched, preferably linear.
  • A2 is a cyclic organic group
  • examples of the cyclic organic group are the same as the cyclic organic groups that Rc6 and Rc7 have as substituents.
  • A2 is an alkoxycarbonyl group
  • examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that Rc6 and Rc7 have as substituents.
  • R c6 and R c7 include alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl groups; 2-methoxyethyl; group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy -n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl group, 7- Alkoxyalkyl groups such as ethoxy-n-heptyl group and 8-ethoxy-n-octyl groups; 2-
  • Alkyl group 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n -heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl- Cycloalkylalkyl groups such as n-hexyl group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group; 2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl
  • R c6 and R c7 are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-hepta It is a fluoro-n-pentyl group.
  • A is S because it is easy to obtain a photopolymerization initiator with excellent sensitivity.
  • R c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group.
  • R c9 in formula (c5) is a monovalent organic group, it can be selected from various organic groups within the range that does not impede the object of the present invention.
  • a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. is more preferred.
  • the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
  • Preferred examples of the organic group represented by Rc9 in formula ( c5 ) include the same monovalent organic groups as Rc5 in formula (c3).
  • R c9 substituted by a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group; benzoyl group; nitro group; optionally substituted benzofuranylcarbonyl group is preferred, benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group a 4-(phenyl)phenylcarbonyl group is more preferred.
  • n4 is preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0 or 1.
  • the position to which R c9 is bonded is preferably para to the bond to which the phenyl group to which R c9 is bonded is bonded to an oxygen atom or a sulfur atom.
  • the monovalent organic group as Rc2 is not particularly limited as long as it does not impair the object of the present invention.
  • a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. is more preferred.
  • the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
  • Preferred examples of monovalent organic groups for Rc2 include the same monovalent organic groups as Rc5 in formula (c3).
  • Rc2 is also preferably a cycloalkylalkyl group, a phenoxyalkyl group optionally having a substituent on the aromatic ring, and a phenylthioalkyl group optionally having a substituent on the aromatic ring.
  • the substituents that the phenoxyalkyl group and the phenylthioalkyl group may have are those in which the phenyl group, the naphthyl group and the heterocyclyl group contained in R c5 in the formula (c3) further have a substituent. It is the same as the base.
  • R c2 is a substituent containing the group represented by HX 2 C— or H 2 XC—, an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or A cycloalkylalkyl group and a phenylthioalkyl group optionally having a substituent on the aromatic ring are preferred.
  • Alkyl group optionally substituted phenyl group, number of carbon atoms in cycloalkyl group contained in cycloalkylalkyl group, number of carbon atoms in alkylene group contained in cycloalkylalkyl group, cycloalkylalkyl group, aromatic Regarding the number of carbon atoms of the alkylene group contained in the phenylthioalkyl group optionally having substituents on the ring, or the phenylthioalkyl group optionally having substituents on the aromatic ring, the formula (c3 ) is the same as R c5 .
  • A3 is a divalent organic group , preferably a divalent hydrocarbon group, preferably an alkylene group.
  • A4 is a monovalent organic group, preferably a monovalent hydrocarbon group.
  • the alkylene group may be linear or branched, preferably linear.
  • the number of carbon atoms in the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.
  • Preferred examples of A 4 include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms.
  • Preferred specific examples of A4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hexyl.
  • Preferable specific examples of the group represented by -A 3 -CO-OA 4 include a 2-methoxycarbonylethyl group, a 2-ethoxycarbonylethyl group, a 2-n-propyloxycarbonylethyl group, a 2-n -butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group , 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-
  • R c2 a group represented by the following formula (c7) or (c8) is also preferable.
  • R c10 and R c11 are each independently a monovalent organic group
  • n5 is an integer of 0 or more and 4 or less
  • R c10 and R c11 may combine with each other to form a ring
  • R c12 is a monovalent organic group
  • n6 is an integer of 1 or less and 8 or less
  • n7 is an integer of 1 or more and 5 or less
  • n8 is an integer from 0 to (n7+3).
  • R c10 and R c11 in formula (c7) are the same as R c8 in formula (c4).
  • R c10 includes a halogenated alkoxy group containing a group represented by HX 2 C-- or H 2 XC--, a halogenated alkyl group containing a group represented by HX 2 C-- or H 2 XC--, an alkyl group, or A phenyl group is preferred.
  • the ring may be either an aromatic ring or an aliphatic ring.
  • n7 is an integer of 0 or more and 4 or less, preferably 0 or 1, more preferably 0.
  • R c12 is an organic group.
  • the organic group include groups similar to the organic groups described for R c8 in formula (c4).
  • alkyl groups are preferred.
  • Alkyl groups may be straight or branched.
  • the number of carbon atoms in the alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less.
  • R c12 is preferably exemplified by a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc. Among these, a methyl group is more preferable.
  • n7 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2.
  • n8 is 0 or more and (n7+3) or less, preferably an integer of 0 or more and 3 or less, more preferably 0 or more and 2 or less, and particularly preferably 0.
  • n8 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.
  • R c3 is a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an optionally substituted aryl group.
  • R c3 is an aliphatic hydrocarbon group, a phenyl group, a naphthyl group and the like are preferably exemplified as the substituent which may be possessed.
  • R c3 is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-cyclopentylethyl group, a 2-cyclobutylethyl group, A cyclohexylmethyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group and the like are preferably exemplified, and among these, a methyl group or a phenyl group is more preferable.
  • Preferable specific examples of the compound represented by formula (c2) and having a group represented by formula (c5) as R c1 include the following compounds.
  • a phosphine oxide compound is also preferable from the viewpoint of good deep-part curability of the photocurable composition.
  • a phosphine oxide compound containing a partial structure represented by the following formula (c9) is preferable.
  • R c21 and R c22 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aliphatic acyl group having 2 to 20 carbon atoms, or an aromatic group having 7 to 20 carbon atoms. group acyl groups. However, both R c21 and R c22 are not aliphatic acyl groups or aromatic acyl groups.
  • the number of carbon atoms in the alkyl groups of R c21 and R c22 is preferably 1 or more and 12 or less, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 4 or less.
  • the alkyl groups as R c21 and R c22 may be linear or branched.
  • alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert- pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, and An n-dodecyl group can be mentioned.
  • the number of carbon atoms in the cycloalkyl groups for R c21 and R c22 is preferably 5 or more and 12 or less.
  • Specific examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl groups.
  • the number of carbon atoms in the aryl groups of R c21 and R c22 is preferably 6 or more and 12 or less.
  • the aryl group may have a substituent. Examples of substituents include halogen atoms, alkyl groups having 1 to 4 carbon atoms, and alkoxy groups having 1 to 4 carbon atoms. Specific examples of aryl groups include phenyl and naphthyl groups.
  • the number of carbon atoms in the aliphatic acyl groups for R c21 and R c22 is 2 or more and 20 or less, preferably 2 or more and 12 or less, more preferably 2 or more and 8 or less, and even more preferably 2 or more and 6 or less.
  • Aliphatic acyl groups may be straight or branched. Specific examples of aliphatic acyl groups include acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, and tetradecanoyl groups. , pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, nonadecanoyl, and icosanoyl groups.
  • the number of carbon atoms in the aromatic acyl groups for R c21 and R c22 is 7 or more and 20 or less.
  • the aromatic acyl group may have a substituent.
  • substituents include halogen atoms, alkyl groups having 1 to 4 carbon atoms, and alkoxy groups having 1 to 4 carbon atoms.
  • Specific examples of aromatic acyl groups include benzoyl, o-tolyl, m-tolyl, p-tolyl, 2,6-dimethylbenzoyl, 2,6-dimethoxybenzoyl, 2,4,6- Trimethylbenzoyl, ⁇ -naphthoyl, and ⁇ -naphthoyl groups are included.
  • phosphine oxide compound containing the structural moiety represented by formula (c9) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, fin oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and the like.
  • cationic polymerization initiator (C2) conventionally known cationic polymerization initiators can be used without particular limitation.
  • Typical examples of the cationic polymerization initiator (C2) include onium salts.
  • the cationic polymerization initiator (C2) includes oxonium salts, ammonium salts, phosphonium salts, sulfonium salts and iodonium salts, preferably sulfonium salts and iodonium salts, more preferably sulfonium salts.
  • the content of the initiator (C) in the photocurable composition is not particularly limited.
  • the content of the initiator (C) is appropriately determined depending on the type of the radically polymerizable group or the cationic polymerizable group and the type of the initiator (C).
  • the content of the initiator (C) in the photocurable composition is 0.01 parts by mass or more and 20 parts by mass when the mass of the photocurable composition excluding the mass of the solvent (S) described later is 100 parts by mass. It is preferably at most parts by mass, more preferably at least 0.1 parts by mass and at most 15 parts by mass, and even more preferably at least 1 part by mass and not more than 10 parts by mass.
  • the photocurable composition may contain a plasticizer (D).
  • the plasticizer (D) is a component that reduces the viscosity of the photocurable composition without significantly impairing the curability of the photocurable composition or the refractive index of the cured product.
  • a compound represented by the following formula (d-1) is preferable as the plasticizer (D).
  • R d1 -R d3 r -X d -R d4 s -R d2 (d-1) (In formula (d-1), R d1 and R d2 are each independently a phenyl group optionally having 1 to 5 substituents, and the substituents have 1 to 4 carbon atoms.
  • R d3 and R d4 are each independently a methylene group or an ethane-1,2-diyl group; , and s are each independently 0 or 1, and X d is an oxygen atom or a sulfur atom.
  • the viscosity of the photocurable composition is lowered without significantly impairing the curability of the photocurable composition and the refractive index of the cured product.
  • the viscosity of the plasticizer (D) measured by an E-type viscometer at 25° C. is preferably 10 cP or less, more preferably 8 cP or less, and even more preferably 6 cP or less.
  • the boiling point of the plasticizer (D) under atmospheric pressure is 250° C. or higher because the plasticizer (D) is difficult to volatilize and the effect of reducing the viscosity of the photocurable composition is easily maintained.
  • the boiling point of the plasticizer (D) under atmospheric pressure is not particularly limited, it may be, for example, 300° C. or lower, or 350° C. or lower.
  • R d1 and R d2 in formula (d-1) are each independently a phenyl group optionally having 1 to 5 substituents.
  • the substituent bonded to the phenyl group is a group selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom.
  • the number of substituents is not particularly limited. The number of substituents is 1 or more and 5 or less, preferably 1 or 2, and preferably 1. From the viewpoint of lowering the viscosity of the photocurable composition, each of R d1 and R d2 is preferably an unsubstituted phenyl group.
  • alkyl group having 1 to 4 carbon atoms as a substituent examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. mentioned.
  • alkoxy groups having 1 to 4 carbon atoms as substituents include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, and tert- A butyloxy group is mentioned.
  • a halogen atom as a substituent includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R d3 and R d4 in formula (d-1) are each independently a methylene group or an ethane-1,2-diyl group. Moreover, r and s are 0 or 1 each independently.
  • X d in formula (d-1) is an oxygen atom or a sulfur atom.
  • Preferred specific examples of the compound represented by formula (d-1) described above include diphenyl ether, diphenyl sulfide, dibenzyl ether, dibenzyl sulfide, diphenethyl ether, and diphenethyl sulfide. Among these, diphenyl sulfide and/or dibenzyl ether are more preferred.
  • the content of the plasticizer (D) in the photocurable composition is 0 mass with respect to the mass of the entire photocurable composition in terms of both viscosity adjustment and dispersibility of the metal oxide fine particles (B). % to 35% by mass or less, and more preferably 5% to 15% by mass.
  • the photocurable composition contains an amine compound (E1) represented by the following formula (e1) and/or the following formula (e2 ) may be included as the nitrogen-containing compound (E).
  • E1 represented by the following formula (e1)
  • e2 the following formula (e2 )
  • NR e1 R e2 R e3 e1
  • R e4 ⁇ N CR e5 R e6 (e2)
  • R e4 , R e5 and R de6 are each independently a hydrogen atom or an organic group.
  • R e1 , R e2 , R e3 , R e4 , R e5 , and R de6 are organic groups
  • the organic groups are within a range that does not impair the desired effect. and can be selected from a variety of organic groups.
  • a carbon atom-containing group is preferable, and one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms. is more preferred.
  • the number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less.
  • Preferred examples of the organic group include an alkyl group, a cycloalkyl group, an optionally substituted phenyl group, an optionally substituted phenylalkyl group, an optionally substituted naphthyl group, An optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, and the like are included.
  • the number of carbon atoms in the alkyl group as the organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 6 or less.
  • the structure of the alkyl group may be linear or branched. Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group and isopentyl group.
  • the alkyl group may contain an ether bond (--O--) in the carbon chain.
  • alkyl groups having an ether bond in the carbon chain examples include methoxyethyl, ethoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, and methoxypropyl groups.
  • the number of carbon atoms in the cycloalkyl group as the organic group is preferably 3 or more and 10 or less, more preferably 3 or more and 6 or less.
  • Specific examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
  • the number of carbon atoms in the phenylalkyl group as the organic group is preferably 7 or more and 20 or less, more preferably 7 or more and 10 or less.
  • the number of carbon atoms in the naphthylalkyl group as the organic group is preferably 11 or more and 20 or less, more preferably 11 or more and 14 or less.
  • Specific examples of phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl groups.
  • naphthylalkyl groups include ⁇ -naphthylmethyl, ⁇ -naphthylmethyl, 2-( ⁇ -naphthyl)ethyl, and 2-( ⁇ -naphthyl)ethyl groups.
  • the phenylalkyl group or naphthylalkyl group may further have a substituent on the phenyl group or naphthyl group.
  • the heterocyclyl group is the same as when R c4 in formula (c3) is a heterocyclyl group, and the heterocyclyl group may further have a substituent.
  • a heterocyclyl group as an organic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group.
  • the heterocyclyl group is preferably a 5- or 6-membered monocyclic ring containing one or more N, S, or O, or a heterocyclyl group in which such monocyclic rings are condensed with each other or such monocyclic rings and a benzene ring are condensed.
  • the heterocyclyl group is a condensed ring, it has up to 3 rings.
  • Heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran; be done.
  • the substituents include alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, group, a halogenated alkyl group having 1 to 6 carbon atoms, a halogenated alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, alkoxycarbonyl group, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, monoalkylamino group having alkyl group having 1 to 6 carbon atoms, dialkylamino group having alkyl group having 1 to 6 carbon atoms , a benzoyl group, a halogen atom, a nitro group, a cyano group, and the like.
  • the number of substituents is not particularly limited, and is preferably 1 to 4.
  • the phenyl group, naphthyl group and heterocyclyl group contained in the organic group have multiple substituents, the multiple substituents may be the same or different.
  • R e1 , R e2 and R e3 are each independently a hydrogen atom or an organic group, and at least one of R e1 , R e2 and R e3 is an aromatic group-containing group.
  • R e4 , R e5 , and R de6 are each independently a hydrogen atom or an organic group, and at least one of R e4 , R e5 , and R de6 is an aromatic group-containing group.
  • the aromatic ring in the aromatic group-containing group may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. A hydrocarbon group is preferable as the aromatic group-containing group.
  • Aromatic hydrocarbon groups include phenyl, naphthalene-1-yl, and naphthalene-2-yl groups. Among these aromatic hydrocarbon groups, a phenyl group is preferred.
  • Aralkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl groups.
  • R e1 , R e2 and R e3 is preferably a group represented by A e1 —CH 2 —.
  • R e4 is preferably a group represented by Ar e1 —CH 2 —.
  • Ar e1 is an aromatic group optionally having a substituent.
  • the aromatic group for Ar e1 may be either an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • the aromatic group for Ar e1 is preferably an aromatic hydrocarbon group.
  • Aromatic hydrocarbon groups include phenyl, naphthalene-1-yl, and naphthalene-2-yl groups. Among these aromatic hydrocarbon groups, a phenyl group is preferred.
  • the substituents that the aromatic group as Ar e1 may have include the organic groups as R e1 , R e2 , R e3 , R e4 , R e5 and R e6 as phenyl group, naphthyl group and heterocyclyl group. In some cases, it is the same as the substituents these groups may have.
  • amine compound represented by formula (e1) include triphenylamine, N,N-diphenylbenzylamine, N-phenyldibenzylamine, tribendialumine, N,N-dimethylphenylamine, N -methyldiphenylamine, N,N-dimethylbenzylamine, N-methyldibenzylamine, N-methyl-N-benzylphenylamine, N,N-diethylphenylamine, N-ethyldiphenylamine, N,N-diethylbenzylamine, N-ethyldibenzylamine, and N-ethyl-N-benzylphenylamine.
  • imine compounds represented by formula (e2) include N-benzylphenylmethanimine, N-benzyldiphenylmethanimine, N-benzyl-1-phenylethanimine, and N-benzylpropane-2-imine. is mentioned.
  • the content of the nitrogen-containing compound in the photocurable composition is not particularly limited as long as the desired effects are not impaired.
  • the content of the nitrogen-containing compound (E) is preferably 5% by mass or more and 25% by mass or less, more preferably 7% by mass or more and 20% by mass or less, relative to the mass of the photopolymerizable compound (A).
  • the photocurable composition may contain a compound represented by the following formula (F1) as the triazine compound (F).
  • R F1 , R F2 and R F3 are each independently a monocyclic aromatic group optionally having a substituent or a condensed aromatic group optionally having a substituent is. However, R F1 , R F2 and R F3 do not contain a radically polymerizable group-containing group or a cationically polymerizable group-containing group. When a monocyclic aromatic group or a condensed aromatic group has substituents, the substituents do not contain an aromatic ring.
  • the three -NH- groups attached to the triazine ring are attached to the aromatic rings in R F1 , R F2 and R F3 respectively.
  • the monocyclic aromatic groups as R F1 , R F2 and R F3 may be aromatic hydrocarbon groups or aromatic heterocyclic groups.
  • Monocyclic aromatic groups include phenyl, pyridinyl, pyridinyl, pyrazinyl, pyridazinyl, furanyl, thienyl, oxazolyl, and thiazolyl groups.
  • substituents that the monocyclic aromatic group may have include halogen atoms, hydroxyl groups, mercapto groups, cyano groups, nitro groups, and monovalent organic groups.
  • the monovalent organic group does not contain an aromatic ring.
  • a halogen atom as a substituent includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Monovalent organic groups include alkyl groups, alkoxy groups, alkoxyalkyl groups, aliphatic acyl groups, aliphatic acyloxy groups, alkoxycarbonyl groups, alkylthio groups, and aliphatic acylthio groups.
  • the number of carbon atoms in the monovalent organic group as a substituent is not particularly limited as long as the desired effect is not impaired.
  • the number of carbon atoms in the monovalent organic group as a substituent is, for example, preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, and even more preferably 1 or more and 8 or less.
  • the lower limit of the number of carbon atoms is 2.
  • alkyl groups as substituents include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include n-hexyl, n-heptyl, and n-octyl groups.
  • alkoxy groups as substituents include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n- Examples include pentyloxy, n-hexyloxy, n-heptyloxy, and n-octyloxy groups.
  • alkoxyalkyl groups as substituents include methoxymethyl group, ethoxymethyl group, n-propyloxymethyl group, n-butyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2- n-propyloxyethyl group, 2-n-butyloxyethyl group, 3-methoxy-n-propyloxy group, 3-ethoxy-n-propyloxy group, 3-n-propyloxy-n-propyloxy group, 3 -n-butyloxy-n-propyloxy group, 4-methoxy-n-butyloxy group, 4-ethoxy-n-butyloxy group, 4-n-propyloxy-n-butyloxy group, 4-n-butyloxy-n-butyloxy groups.
  • aliphatic acyl groups as substituents include acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, and octanoyl group.
  • aliphatic acyloxy groups as substituents include acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, and octanoyloxy groups.
  • alkoxycarbonyl groups as substituents include methoxycarbonyl, ethoxycarbonyl, n-propyloxycarbonyl, isopropyloxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl and sec-butyloxy. carbonyl, tert-butyloxycarbonyl, n-pentyloxycarbonyl, n-hexyloxycarbonyl, n-heptyloxycarbonyl, and n-octyloxycarbonyl groups.
  • alkylthio groups as substituents include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio and n-pentylthio. , n-hexylthio, n-heptylthio, and n-octylthio groups.
  • aliphatic acylthio groups as substituents include an acetylthio group, a propionylthio group, a butanoylthio group, a pentanoylthio group, a hexanoylthio group, a heptanoylthio group, and an octanoylthio group.
  • the number of substituents is not particularly limited as long as the desired effect is not impaired.
  • the number of substituents is preferably 1 or more and 4 or less, more preferably 1 or 2, and particularly preferably 1.
  • the multiple substituents may be different from each other.
  • Examples of the monocyclic aromatic group which may have a substituent explained above include a phenyl group, a 4-cyanophenyl group, a 3-cyanophenyl group, a 2-cyanophenyl group, a 2,3-dicyanophenyl group, 2,4-dicyanophenyl group, 2,5-dicyanophenyl group, 2,6-dicyanophenyl group, 3,4-dicyanophenyl group, 3,5-dicyanophenyl group, 4-nitrophenyl group, 3-nitrophenyl group, 2-nitrophenyl group, 4-chlorophenyl group, 3-chlorophenyl group, 2-chlorophenyl group, 4-bromophenyl group, 3-bromophenyl group, 2-bromophenyl group, 4-iodophenyl group, 3-iodo phenyl, 2-iodophenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphen
  • phenyl group, 4-cyanophenyl group, 3-cyanophenyl group, 2-cyanophenyl group, 4-nitrophenyl group, 3-nitrophenyl group and 2-nitrophenyl group are preferred, and phenyl and 4-cyanophenyl groups are more preferred.
  • the condensed aromatic groups as R F1 , R F2 and R F3 are groups obtained by removing one hydrogen atom from a condensed polycyclic ring in which two or more aromatic single rings are condensed.
  • the number of aromatic monocyclic rings that constitute the condensed aromatic group is not particularly limited.
  • the number of aromatic monocyclic rings constituting the condensed aromatic group is preferably 2 or 3, more preferably 2. That is, the condensed aromatic group is preferably a bicyclic condensed aromatic group or a tricyclic condensed aromatic group, more preferably a bicyclic condensed aromatic group.
  • the condensed aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • Bicyclic fused aromatic groups include, for example, naphthalene-1-yl group, naphthalene-2-yl group, quinolin-2-yl group, quinolin-3-yl group, quinolin-4-yl group, quinolin-5 -yl group, quinolin-6-yl group, quinolin-7-yl group, quinolin-8-yl group, isoquinolin-1-yl, isoquinolin-3-yl group, isoquinolin-4-yl group, isoquinolin-5-yl group, isoquinolin-6-yl group, isoquinolin-7-yl group and isoquinolin-8-yl group, benzoxazol-2-yl group, benzoxazol-4-yl group, benzoxazol-5-yl group, benzoxazole -6-yl group, benzoxazol-7-yl group, benzothiazol-2-yl group, benzothiazol-4-yl group,
  • tricyclic condensed aromatic groups examples include anthracen-1-yl group, anthracen-2-yl group, anthracen-9-yl group, phenanthrene-1-yl group, phenanthrene-2-yl group, phenanthrene-3 -yl group, phenanthren-4-yl group, phenanthren-9-yl group, acridin-1-yl group, acridin-2-yl group, acridin-3-yl group, acridin-4-yl group, and acridin-9 -yl group.
  • the substituents that the polycyclic condensed aromatic group such as the bicyclic condensed aromatic group and the tricyclic condensed aromatic group may have are the substituents that the monocyclic aromatic group may have. It is the same.
  • naphthalene-1-yl group naphthalene-2-yl group, quinolin-2-yl group, quinolin-3-yl group, quinoline -4-yl group, quinolin-5-yl group, quinolin-6-yl group, quinolin-7-yl group, quinolin-8-yl group, benzothiazol-2-yl group, 2-mercaptobenzothiazol-6- An yl group is preferred.
  • a naphthalene-1-yl group a quinolin-3-yl group, a quinolin-4-yl group, and a 2-mercaptobenzothiazol-6-yl group are preferred, and a naphthalen-1-yl group is more preferred.
  • R F1 , R F2 , and one or two of R F3 is an optionally substituted naphthyl group, and one or two of R F1 , R F2 and R F3 are a 4-cyanophenyl group or benzothiazolyl Compounds that are radicals are preferred.
  • a naphthalene-1-yl group is preferable as the naphthyl group which may have a substituent.
  • Suitable specific examples of the compound represented by formula (F1) include the compound of the following formula.
  • the method for producing the compound represented by formula (F1) is not particularly limited. Typically, it can be produced by reacting a cyanuric halide such as cyanuric chloride with an aromatic amine represented by R F1 —NH 2 , R F2 —NH 2 and R F3 —NH 2 . These plural types of amines may be reacted with the cyanuric halide simultaneously or sequentially, preferably sequentially with the cyanuric halide.
  • the compound represented by formula (F1) is usually synthesized in an organic solvent.
  • an organic solvent is not particularly limited as long as it is an inert solvent that does not react with cyanuric halides, aromatic amines, radically polymerizable groups, cationic polymerizable groups, and the like.
  • an organic solvent or the like exemplified as a specific example of the solvent (S) can be used.
  • cyanuric halide and aromatic amines such as aromatic amines represented by R F1 —NH 2 , R F2 —NH 2 and R F3 —NH 2
  • the reaction temperature is preferably from 0°C to 150°C.
  • the content of the triazine compound (F) in the photocurable composition is not particularly limited as long as the desired effects are not impaired.
  • the content of the triazine compound (F) in the photocurable composition is, for example, 0.1 parts by mass when the mass of the photocurable composition excluding the mass of the solvent (S) described later is 100 parts by mass. 30 parts by mass or less is preferable, 0.3 parts by mass or more and 20 parts by mass or less is more preferable, and 0.5 parts by mass or more and 15 parts by mass or less is even more preferable.
  • the photocurable composition contains a solvent (S) for the purpose of adjusting coatability.
  • the solvent (S) has the following formula (S1): R S2 -O-(R S1 -O) ns -R S3 (S1) (In formula (S1), R S1 is an alkylene group having 2 to 4 carbon atoms; R S2 and R S3 are each a hydrogen atom, a methyl group, or an ethyl group; R S2 and R S3 is not a hydrogen atom at the same time, and ns is an integer of 1 or more and 4 or less.) A plurality of solvents (S1) represented by are included. The value of the Hildebrand solubility parameter of the solvent (S1) is 21.0 MPa 0.5 or less.
  • the photocurable composition By including the solvent (S1) as the solvent (S) in the photocurable composition, even if the photocurable composition contains the metal oxide fine particles (B) at a high concentration, the metal oxide fine particles ( B) is well dispersed in the photocurable composition and has good wettability to the substrate to which the photocurable composition is applied. Moreover, since the photocurable composition contains the solvent (S1) as the solvent (S), the photocurable composition is less likely to dry rapidly. In this regard, in the inkjet method, it is required that the ink does not thicken or solidify due to drying in the head for a long period of time. As described above, the photocurable composition containing the solvent (S1) as the solvent (S) is less likely to dry rapidly, and thus can be suitably used in the inkjet method.
  • the value of the Hildebrand solubility parameter of the solvent (S1) is preferably 17.0 MPa 0.5 or more, more preferably 18.0 MPa 0.5 or more, in terms of easily obtaining the desired effect by using the solvent (S1). , 18.5 MPa 0.5 or more is more preferable.
  • R 1 S1 is an alkylene group having 2 or more and 4 or less carbon atoms.
  • alkylene groups having 2 to 4 carbon atoms include ethane-1,2-diyl group (ethylene group), propane-1,3-diyl group, propane-1,2-diyl group), butane-1,4 -diyl group, butane-1,2-diyl group and butane-1,3-diyl group are preferred, and ethane-1,2-diyl group and propane-1,2-diyl group are more preferred.
  • the solvent (S) may contain, together with the solvent (S1), another solvent (S2) that does not correspond to the solvent (S1).
  • Other solvents (S2) include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono- n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether (HO—CH 2 CH 2 CH 2 —O—CH 3 ), propylene glycol monomethyl ether ( HO--C(CH 3 )HCH 2 --O--CH 3 , or H 3 C--O--C(CH 3 )HCH 2 --OH), propylene glycol monoethyl ether (
  • the ratio of the mass of the solvent (S1) to the mass of the solvent (S) is preferably 20% by mass or more, more preferably 30% by mass or more, in terms of easily obtaining the desired effect by using the solvent (S1). , more preferably 50% by mass or more, even more preferably 70% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass.
  • the upper limit of the ratio of the mass of the solvent (S1) to the mass of the solvent (S) is not particularly limited.
  • the upper limit of the ratio of the mass of the solvent (S1) to the mass of the solvent (S) may be, for example, 100% by mass or less, 90% by mass or less, or 70% by mass or less. , 50% by mass or less, and may be 30% by mass or less.
  • composition ratio in the case of using the solvent (S1) and the solvent (S2) as the solvent (S) depends on the effect of the present invention described above, the uniformity of the photocurable composition, or the photocurable composition.
  • (S1):(S2) is preferably 99:1 to 25:75, more preferably 95:5 to 35, in terms of suppressing the generation of voids when forming a film on a fine trench pattern using :65 is more preferred.
  • the composition ratio of the solvent (S1) is (S1- H): (S1-L) is, for example, 99:1 to 1:99 as a mass ratio, and the above-mentioned effect of the present invention, uniformity of the photocurable composition, or photocurability From the viewpoint of suppressing the generation of voids when forming a film on a fine trench pattern using the composition, the ratio is preferably 99:1 to 30:70, more preferably 95:5 to 40:60, and 90 :10 to 70:30 is more preferable.
  • the content of the solvent (S) is preferably an amount such that the solid content concentration of the photocurable composition is 1% by mass or more and 99% by mass or less, more preferably 5% by mass or more and 50% by mass or less, and 10% by mass. % or more and 30 mass % or less is more preferable.
  • the photocurable composition may contain various additives as components other than the above components.
  • Additives include sensitizers, curing accelerators, fillers, dispersants, adhesion promoters such as silane coupling agents, antioxidants, aggregation inhibitors, thermal polymerization inhibitors, antifoaming agents, surfactants, etc. are mentioned.
  • the amount of these additives to be used is appropriately determined in consideration of the amount of these additives normally used in the photocurable composition.
  • a cured product After molding the photocurable composition described above into a desired shape, a cured product can be produced by exposing the photocurable composition to light according to the type of the initiator (C).
  • the cured product produced by the above method exhibits a high refractive index of, for example, preferably 1.70 or more, more preferably 1.90 or more, at a wavelength of 520 nm. Therefore, the cured product produced by the above method is suitably used in optical applications requiring a high refractive index.
  • a cured film made of a cured product of the photocurable composition described above is suitably used as a high refractive index film constituting an antireflection film or the like in various display panels such as an organic EL display panel and a liquid crystal display panel. be.
  • the method for molding the photocurable composition is not particularly limited, and is appropriately selected according to the shape of the cured product.
  • Examples of the molding method include coating and casting into a mold.
  • a method for producing a cured film will be described as a representative example of the method for producing a cured product.
  • the photocurable composition is applied onto a desired substrate to form a coating film, and then, if necessary, at least part of the solvent (S) is removed from the coating film to form a coating film.
  • the method of applying the photocurable composition onto the substrate is not particularly limited.
  • the curable composition is applied to the substrate using a contact transfer coating device such as a roll coater, reverse coater, bar coater, or slit coater, or a non-contact coating device such as a spinner (rotary coating device) or curtain flow coater.
  • a coating film can be formed by coating on the substrate so as to have a desired film thickness.
  • a printing method such as a screen printing method or an inkjet printing method can be applied.
  • the photocurable composition described above dries rapidly and is less likely to thicken or solidify in an inkjet head. Therefore, by using the above-described photocurable composition, it is possible to satisfactorily perform coating by an inkjet printing method.
  • the coating film After coating the photocurable composition on the substrate, it is preferable to bake the coating film as necessary to remove at least part of the solvent (S) from the coating film.
  • the baking temperature is appropriately determined in consideration of the boiling point of the solvent (S) and the like. Baking may be performed at low temperature under reduced pressure conditions.
  • the baking method is not particularly limited, and includes, for example, a method of drying using a hot plate at a temperature of 80°C to 150°C, preferably 85°C to 120°C for 60 seconds to 500 seconds.
  • the thickness of the coating film formed as described above is not particularly limited.
  • the film thickness of the coating film is appropriately determined according to the intended use of the cured film.
  • the thickness of the coating film is typically adjusted as appropriate so that a cured film having a thickness of preferably 0.1 ⁇ m or more and 10 ⁇ m or less, more preferably 0.2 ⁇ m or more and 5 ⁇ m or less is formed.
  • a cured film can be obtained by exposing the coating film after forming the coating film by the above method.
  • the conditions for exposing the coating film are not particularly limited as long as the curing progresses satisfactorily. Exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer laser light. Although there is no particular limitation on the energy dose to be irradiated, for example, 30 mJ/cm 2 or more and 5000 mJ/cm 2 or less can be mentioned. After exposure, the exposed coating film may be baked by the same method as heating after coating.
  • Example 1 to 15 and Comparative Examples 1 to 11 In Examples 1 to 15 and Comparative Examples 1 to 11, the following A-1 to A-4 were used as the photopolymerizable compound (A).
  • A-1 A compound having the following structure
  • A-2 Compound A-2 obtained in Synthesis Example 1
  • A-3 Compound A-3 obtained in Synthesis Example 2
  • A-4 2-(phenylthio)ethyl acrylate
  • Examples 1 to 15 and Comparative Examples 1 to 11 titanium oxide fine particles synthesized by a known hydrothermal method and using methoxy(triethyleneoxy)propyltrimethoxysilane as a capping agent were used as the metal oxide fine particles (B). (particle size measured by TEM: about 7 nm) was used.
  • S-1 to S-3 were used as the aforementioned solvent (S1).
  • S-1 HO—(CH 2 CH 2 CH 2 —O) 2 —CH 3 (dipropylene glycol monomethyl ether, Hildebrand solubility parameter: 20.1 MPa 0.5 )
  • S-2 H 3 CO—(CH 2 CH 2 —O) 3 —CH 3 (triethylene glycol dimethyl ether, Hildebrand solubility parameter: 18.4 MPa 0.5 )
  • S-3 HO—(C(CH 3 )HCH 2 —O) 3 —CH 3 (tripropylene glycol monomethyl ether, Hildebrand solubility parameter: 19.1 MPa 0.5 )
  • S-4 to S-13 were used as the aforementioned other solvent (S2).
  • S-4 Propylene glycol monomethyl ether acetate (Hildebrand solubility parameter: 18.3 MPa 0.5 )
  • S-5 3-phenoxytoluene (Hildebrand solubility parameter: 19.7 MPa 0.5 )
  • S-6 triethylene glycol mono-n-butyl ether (Hildebrand solubility parameter: 19.6 MPa 0.5 )
  • S-7 H 3 CH 2 CH 2 CO—(C(CH 3 )HCH 2 —O) 2 —CH 3 (dipropylene glycol methyl-n-propyl ether, Hildebrand solubility parameter: 16.8 MPa 0.
  • S-8 H 3 CH 2 CH 2 CH 2 CO—(C(CH 3 )HCH 2 —O) 2 —CH 3 (dipropylene glycol methyl-n-butyl ether, Hildebrand solubility parameter: 16.8 MPa 0 .5 )
  • S-9 Diethylene glycol mono-n-butyl ether (Hildebrand solubility parameter: 19.7 MPa 0.5 )
  • S-10 triethylene glycol monoethyl ether (Hildebrand solubility parameter: 21.6 MPa 0.5 )
  • S-11 diethylene glycol mono-n-hexyl ether (Hildebrand solubility parameter: 19.8 MPa 0.5 )
  • S-12 Diethylene glycol monobutyl ether acetate (Hildebrand solubility parameter: 18.1 MPa 0.5 )
  • S-13 1,6-hexanediol diacetate (Hildebrand solubility parameter: 18.3 MPa 0.5 )
  • the photocurable compositions of Example 15 and Comparative Example 11 were obtained by dissolving and dispersing in the solvent (S) of the type shown in Table 1 as follows. Using the obtained photocurable composition, according to the following methods, measurement of the refractive index of the cured film, evaluation of the dispersion stability of the curable composition, evaluation of the wettability of the photocurable composition, and light Evaluation of dryness of the curable composition and evaluation of voids were performed. These measurement results and evaluation results are shown in Tables 1 and 2.
  • the film composed of the cured product is heated at 110° C. for 2 minutes to form a coated film having a thickness of 1 ⁇ m. got The coating film thus obtained was exposed to light using a high-pressure mercury lamp so that the cumulative exposure amount was 100 mJ/cm 2 .
  • the coated film after exposure was heated at 110° C. for 2 minutes to obtain a cured film with a thickness of 1 ⁇ m.
  • the refractive index of the resulting cured film was measured using a prism coupler manufactured by Metricon to determine the refractive index of the cured film at a wavelength of 520 nm.
  • the contact angle of the solvent (S) contained in the photocurable composition on the substrate having TiO 2 formed thereon was evaluated as the wettability of the photocurable composition.
  • Dropmaster 700 manufactured by Kyowa Interface Science Co., Ltd.
  • the contact angle of the solvent (S) was measured as the contact angle after 1000 milliseconds of dropping.
  • the average value of the contact angles at three points on the substrate on which TiO 2 was deposited was adopted as the contact angle.
  • C The contact angle is 3° or more.
  • the weight loss rate of the solvent (S) contained in the photocurable composition when heated at 100° C. under atmospheric pressure was evaluated as the drying property of the photocurable composition. Specifically, first, a glass substrate whose surface was cleaned with acetone was prepared. 0.3 g of the solvent (S) contained in the photocurable composition of each example and each comparative example was placed on the cleaned surface of the prepared glass substrate. The glass substrate with droplets of the solvent (S) is placed on a hot plate at 100 ° C., and the solution of the solvent (S) on the glass substrate is added every 3 minutes from the time of placement until 30 minutes after placement. The drops were weighed.
  • the obtained elapsed time (minutes) from placement and the weight of the droplet of the solvent (S) are measured using Microsoft (registered trademark) Excel (registered trademark), with the elapsed time from placement as the horizontal axis and the solvent
  • a scatter diagram was obtained by plotting the droplet weight of (S) on a coordinate plane with the vertical axis.
  • linear approximation was performed using the function of Microsoft (registered trademark) Excel (registered trademark).
  • the slope value (g/min) of the straight line obtained by linear approximation dryness was evaluated according to the following criteria.
  • a + The slope is 0.10 g/min or less.
  • C The slope is 0.30 g/min or more.
  • Void evaluation was performed on the composition of each example and comparative example, which was evaluated as good (A) in dispersion stability. Using a substrate having a trench pattern and the photocurable compositions of Examples and Comparative Examples, cross-sectional samples were prepared under the same film formation conditions as for measuring the refractive index, and the trench pattern was analyzed by a scanning electron microscope (SEM). The presence or absence of voids inside was confirmed and evaluated according to the following criteria. Preferably, no voids are observed even for trench patterns with high aspect ratios. A: No voids are observed in the trench pattern with a width of 60 nm and a depth of 200 nm. C: Voids are observed in the trench pattern with a width of 60 nm and a depth of 200 nm.
  • the metal oxide fine particles (B) are favorably obtained even when the metal oxide fine particles (B) are contained at a high concentration. It can be seen that a photocurable composition that is dispersed and has good wettability with respect to the substrate to be coated can be obtained.

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WO2024181199A1 (ja) * 2023-02-27 2024-09-06 住友化学株式会社 硬化性組成物及び硬化膜

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