Composition, cured product, display device and solid-state imaging device

Abstract

Provided is a novel composition which is capable of providing a cured product exhibiting a high refractive index and has excellent curability. The present invention relates to a composition containing a compound represented by formula (I) and a resin having a refractive index of 1.60 or more at a wavelength of 550 nm. In formula (I), n represents an arbitrary integer of 0-6, L represents a single bond or a divalent group, a plurality of L may be the same or different, R11 represents a monovalent substituent, when a plurality of R11 are present, the plurality of R11 may be the same or different, R12 is selected from the group consisting of a hydrogen atom, formula (1a), and formula (1b), and the plurality of R12 may be the same or different. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a composition and also to a cured product of the composition, a display device including the cured product, and a solid-state imaging device including the cured product. Background Art

[0002] In the field of optical devices, high refractive materials are eagerly desired. A lens can be obtained using a high refractive material, and a light path in an optical device can be controlled using the lens. In solid-state imaging devices, lenses are used for the purpose of improving the efficiency of focusing light into each photoelectric conversion element, and in display devices, lenses are used for the purpose of improving the efficiency of extracting light from pixels. In the past, various high refractive materials have been developed (for example, Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2011 / 102258 Summary of the invention

[0006] Problems to be solved by the invention

[0007] One object of the present invention is to provide a novel composition that can provide a cured product showing a high refractive index and has excellent curability. Another object of the present invention is to provide a cured product of the composition, a display device including the cured product, and a solid-state imaging device including the cured product.

[0008] Means for solving problems

[0009] The present invention includes the following contents.

[0010] [1] A composition comprising a compound represented by formula (I) and a resin having a refractive index of 1.60 or more at a wavelength of 550 nm.

[0011]

[0012] [In formula (I),

[0013] n represents any integer from 0 to 6,

[0014] L represents a single bond or a divalent group. Multiple Ls may be the same or different.

[0015] R 11 represents a monovalent substituent, R 11 When there are multiple R 11 Can be the same or different,

[0016] R 12A plurality of R is selected from the group consisting of a hydrogen atom, formula (1a), and formula (1b). 12 Can be the same or different.

[0017]

[0018] In formula (1a),

[0019] A represents an O atom or a S atom. In formula (I), when there are multiple A's, the multiple A's may be the same or different.

[0020] m a represents 0 or 1, in formula (I), m a When there are multiple m a Can be the same or different,

[0021] R 2 represents a hydrogen atom or a monovalent substituent, R 2 When there are multiple R 2 Can be the same or different,

[0022] * indicates a bond to L.

[0023] In formula (1b),

[0024] R 13 represents a monovalent substituent, R 13 When there are multiple R 13 Can be the same or different,

[0025] * indicates the bond to L. ]

[0026] [2] The composition according to [1], wherein the resin contains a polymerizable group selected from the group consisting of a (meth)acryloyl group, a mercapto group, a cyclic ether group having 2 to 4 carbon atoms, and a cyclic thioether group having 2 to 4 carbon atoms.

[0027] [3] The composition according to [1] or [2], wherein the resin is a resin represented by formula (A).

[0028]

[0029] [In formula (A),

[0030] R represents a monovalent hydrocarbon group. When there are multiple Rs, the multiple Rs may be the same or different.

[0031] n is the average value and represents a number greater than 1,

[0032] A represents an O atom or a S atom, and a plurality of A's may be the same or different.]

[0033] [4] The composition according to any one of [1] to [3], further comprising a polymerization initiator.

[0034] [5] The composition according to any one of [1] to [4], wherein the compound represented by formula (I) comprises a plurality of R 12 A compound represented by formula (1a).

[0035] [6] A cured product of the composition according to any one of [1] to [5].

[0036] [7] A display device comprising the cured product described in [6].

[0037] [8] A solid-state imaging device comprising the cured product described in [6].

[0038] Effects of the Invention

[0039] A novel composition can be provided that can provide a cured product having a high refractive index and excellent curability. In addition, a cured product of the composition, a display device including the cured product, and a solid-state imaging device including the cured product can be provided. DETAILED DESCRIPTION

[0040] <Composition>

[0041] The composition of the present invention (hereinafter also referred to as "composition (I)") comprises a compound represented by formula (I) (hereinafter also referred to as "compound (I)") and a resin having a refractive index of 1.60 or more at a wavelength of 550 nm (hereinafter also referred to as "resin (I)"). Since the composition (I) comprises the compound (I) and the resin (I), a cured product showing a high refractive index can be provided, and in addition, excellent curability can be exhibited. The composition (I) may comprise two or more compounds (I). The composition (I) may comprise two or more resins (I). The composition (I) may comprise a compound (I), a resin (I), and other components in addition thereto. By curing the composition (I), a molded product comprising the cured product of the composition (I) can be formed. The molded product comprising the above-mentioned cured product is an article comprising the above-mentioned cured product, and refers to an article molded into a desired shape.

[0042] <Compound (I)>

[0043] Compound (I) is a compound represented by formula (I).

[0044]

[0045] [In formula (I),

[0046] n represents any integer from 0 to 6,

[0047] L represents a single bond or a divalent group. Multiple Ls may be the same or different.

[0048] R 11 represents a monovalent substituent, R 11 When there are multiple R 11 Can be the same or different,

[0049] R 12 A plurality of R is selected from the group consisting of a hydrogen atom, formula (1a), and formula (1b). 12 Can be the same or different.

[0050]

[0051] In formula (1a),

[0052] A represents an O atom or a S atom. In formula (I), when there are multiple A's, the multiple A's may be the same or different.

[0053] m a represents 0 or 1, in formula (I), m a When there are multiple m a Can be the same or different,

[0054] R 2 represents a hydrogen atom or a monovalent substituent, R 2 When there are multiple R 2 Can be the same or different,

[0055] * indicates a bond to L.

[0056] In formula (1b),

[0057] R 13 represents a monovalent substituent, R 13 When there are multiple R 13 Can be the same or different,

[0058] * indicates the bond to L. ]

[0059] Formula (I) indicates that the two groups represented by the following formulae may be bonded to any of the 1-4 positions or the 5-8 positions of the naphthalene ring. Alternatively, one group may be bonded to any of the 1-4 positions of the naphthalene ring and the other group may be bonded to any of the 5-8 positions of the naphthalene ring. 11 The same is true for .

[0060] -SLR 12

[0061] L represents a single bond or a divalent group. As two Ls representing a divalent group, each independently includes a divalent aliphatic chain hydrocarbon group which may have a substituent, a divalent alicyclic hydrocarbon group which may have a substituent, a divalent aromatic hydrocarbon group which may have a substituent, and a divalent group formed by a combination of these (such as an aralkylene group). The -CH 2 - can be replaced by -O-, -S-, -NR 1A -(R 1A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, -SO 2 -.

[0062] As the divalent aliphatic chain hydrocarbon group, for example, a saturated or unsaturated aliphatic chain hydrocarbon group can be mentioned, and specifically, an alkane diyl such as methylene, ethylene, propane diyl, butane diyl, pentane diyl, hexane diyl, heptane diyl, octane diyl, nonane diyl, decane diyl, undecane diyl, dodecane diyl, tridecane diyl, tetradecane diyl, pentadecane diyl, hexadecane diyl, heptadecandiyl, octadecane diyl, nonadecandiyl, eicosane diyl, etc. can be mentioned. The divalent aliphatic chain hydrocarbon group can be straight chain or branched. The number of carbon atoms in the divalent aliphatic chain hydrocarbon group is usually 1 to 20, preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 or 2.

[0063] Examples of the substituent which the divalent aliphatic chain hydrocarbon group may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a hydroxyl group, an amino group, an acetyl group, and a cyano group.

[0064] Examples of the divalent alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups, and specifically, monocyclic alicyclic hydrocarbon groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cyclooctanediyl, cyclononanediyl, and cyclodecanediyl; and polycyclic alicyclic hydrocarbon groups such as bicyclo[1.1.0]butanediyl, tricyclo[2.2.1.0]heptanediyl, bicyclo[3.2.1]octanediyl, bicyclo[2.2.2.]octanediyl, adamantanediyl, bicyclo[4.3.2]undecanediyl, and tricyclo[5.3.1.1]dodecanediyl. The number of carbon atoms in the divalent alicyclic hydrocarbon group is usually 3 to 20, preferably 3 to 10, more preferably 3 to 6, and even more preferably 5 or 6.

[0065] Examples of the substituent that the divalent alicyclic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, halogen atoms such as fluorine, chlorine, bromine and iodine atoms, hydroxyl, amino, acetyl and cyano groups.

[0066] The divalent aromatic hydrocarbon group may be monocyclic or polycyclic, and examples thereof include phenylene, naphthylene, anthracenediyl, fluorenediyl, etc. The divalent aromatic hydrocarbon group usually has 6 to 20 carbon atoms, and preferably 6 to 10 carbon atoms.

[0067] Examples of the substituent that the divalent aromatic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, halogen atoms such as fluorine, chlorine, bromine and iodine atoms, hydroxyl, amino, acetyl and cyano groups.

[0068] For example, at least one of the two L groups is a single bond or an alkanediyl group, and more preferably both of them are single bonds or alkanediyl groups. In this case, the alkanediyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 or 2.

[0069] The two n are each independently any integer of 0 to 3, preferably any integer of 0 to 2, and more preferably 0 or 1. It is further preferred that both of the two n are 0.

[0070] R as a monovalent substituent 11 , in R 11 When there are a plurality of such groups, each independently includes, for example, a monovalent hydrocarbon group such as a monovalent aliphatic chain hydrocarbon group which may have a substituent, a monovalent alicyclic hydrocarbon group which may have a substituent, a monovalent aromatic hydrocarbon group which may have a substituent, and a monovalent group formed by a combination thereof (such as an aralkyl group); a hydroxyl group; an amino group which may be substituted with one or two alkyl groups having 1 to 6 carbon atoms, such as an amino group, a monomethylamino group, a monoethylamino group, a dimethylamino group, a diethylamino group, and a methylethylamino group; a heterocyclic group such as an aliphatic heterocyclic group having 4 to 20 carbon atoms, or an aromatic heterocyclic group having 3 to 20 carbon atoms, such as a pyrrolidinyl group, a pyrrolinyl group, an imidazolidinyl group, an imidazolinyl group, an oxazolinyl group, a thiazolyl group, a piperidinyl group, a morpholinyl group, a piperazinyl group, an indolyl group, an isoindolyl group, a quinolyl group, a thienyl group, a pyrrolyl group, and a furyl group; a halogen atom; a nitro group; a cyano group; a carboxyl group; a sulfone group; a thiol group; a formyl group; -SF 3 Base; -SF 5 -CH 2 - can be replaced by -O-, -S-, -NR 1B -(R 1B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, -SO 2 -. It should be noted that -CH 2Examples of the group obtained by replacing - with -O- include alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy and octyloxy; and alkoxyalkyl groups such as methoxymethyl, ethoxymethyl and methoxyethyl.

[0071] As the monovalent aliphatic chain hydrocarbon group, for example, a saturated or unsaturated aliphatic chain hydrocarbon group can be mentioned, and specifically, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc. can be mentioned. The monovalent aliphatic chain hydrocarbon group can be straight-chain or branched. The number of carbon atoms in the monovalent aliphatic chain hydrocarbon group is usually 1 to 20, preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 or 2.

[0072] Examples of the substituent which the monovalent aliphatic chain hydrocarbon group may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a hydroxyl group, an amino group, an acetyl group, and a cyano group.

[0073] Examples of the monovalent alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups, specifically, monocyclic alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl; and polycyclic alicyclic hydrocarbon groups such as bicyclo[1.1.0]butyl, tricyclo[2.2.1.0]heptyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2.]octyl, adamantyl, bicyclo[4.3.2]undecyl, and tricyclo[5.3.1.1]dodecyl. The number of carbon atoms in the monovalent alicyclic hydrocarbon group is usually 3 to 20, preferably 3 to 10, more preferably 3 to 6, and even more preferably 5 or 6.

[0074] Examples of the substituent that the monovalent alicyclic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, halogen atoms such as fluorine, chlorine, bromine and iodine atoms, hydroxyl, amino, acetyl and cyano groups.

[0075] The monovalent aromatic hydrocarbon group may be monocyclic or polycyclic, and examples thereof include phenyl, naphthyl, anthracenyl, fluorenyl, etc. The monovalent aromatic hydrocarbon group usually has 6 to 20 carbon atoms, and preferably 6 to 10 carbon atoms.

[0076] Examples of the substituent that the monovalent aromatic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, halogen atoms such as fluorine, chlorine, bromine and iodine atoms, hydroxyl, amino, acetyl and cyano groups.

[0077] R 12 A plurality of R is selected from the group consisting of a hydrogen atom, formula (1a), and formula (1b). 12 They may be the same or different. It is preferred that the compound (I) contains a curable compound (I).

[0078] In formula (I), there are multiple R 12 Examples of the compound represented by a hydrogen atom include a compound represented by formula (IB).

[0079]

[0080] In formula (I), there are multiple R 12 Examples of the compound represented by formula (1b) include compounds represented by formula (IC).

[0081]

[0082] In formula (I), there are multiple R 12 In the case of a compound represented by formula (1a), R 12 The L connected is preferably an alkanediyl group. The compound (I) preferably comprises a plurality of R 12 A compound represented by formula (1a).

[0083] In formula (1a), the two m a Each independently represents 0 or 1, preferably 0. More preferably, 2 m a Both are 0.

[0084] In formula (1a), R 2 represents a hydrogen atom or a monovalent substituent, and there are multiple R 2 They may be the same or different, but are preferably the same. Specific examples of the monovalent substituent include 11 The same monovalent substituent. 2 R 2 Each independently is preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group, more preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group having 1 to 6 carbon atoms, further preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom, a methyl group or an ethyl group.

[0085] There are multiple R in formula (I) 12The compound represented by formula (1a) is represented by the following formula (IA).

[0086]

[0087] In formula (IA), L, R 11 , R 2 , A, n, m a The compounds represented by formula (IA) include the following compounds.

[0088]

[0089] In formula (Ia-1), formula (Ia-2), formula (Ib-1), formula (Ib-2), formula (Ic-1), formula (Ic-2), formula (Id-1), formula (Id-2), formula (Ie-1), and formula (Ie-2), at least one of the two Ls is preferably an alkanediyl group, and both are more preferably alkanediyl groups. In this case, the number of carbon atoms in the alkanediyl group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 or 2.

[0090] In Formula (Ia-1), Formula (Ia-2), Formula (Ib-1), Formula (Ib-2), Formula (Ic-1), Formula (Ic-2), Formula (Id-1), Formula (Id-2), Formula (Ie-1), and Formula (Ie-2), two m a Each independently represents 0 or 1, preferably 0. More preferably, 2 m a Both are 0.

[0091] The two n are each independently any integer of 0 to 3, preferably any integer of 0 to 2, and more preferably 0 or 1. It is further preferred that both of the two n are 0.

[0092] In the formula (Ia-1), formula (Ia-2), formula (Ib-1), formula (Ib-2), formula (Ic-1), formula (Ic-2), formula (Id-1), formula (Id-2), formula (Ie-1), and formula (Ie-2), two R 2 Each independently is preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group, more preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group having 1 to 6 carbon atoms, further preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, a methyl group or an ethyl group. 2 Preferably the same.

[0093] Specific examples of the compound represented by formula (IA) are shown below, but the present invention is not limited thereto.

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] From the viewpoint of synthesis, the molecular weight of compound (I) is preferably 2000 or less, more preferably 1000 or less, and further preferably 500 or less. From the viewpoint of volatility, the molecular weight is preferably 50 or more, more preferably 100 or more, and further preferably 150 or more.

[0105] The content of compound (I) in composition (I) is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 5% by mass or more, preferably 99% by mass or less, more preferably 95% by mass or less, and may be 90% by mass or less or 80% by mass or less, relative to the total amount of solid components of composition (I).

[0106] The total amount of the solid content of the composition (I) refers to the total amount of the components contained in the composition (I) except the solvent. The content of each component in the solid content of the composition can be measured by known analytical methods such as liquid chromatography or gas chromatography. The content of each component in the solid content of the composition (I) can also be calculated based on the formulation when the composition is prepared.

[0107] <Method for producing compound (I)>

[0108] R 12 The compound (I) having a group represented by the formula (1a) can be produced by a method comprising the first step or the first and second steps shown below.

[0109] Step 1: a step of reacting a compound represented by formula (II) with a compound represented by formula (III) to obtain a compound represented by formula (I) wherein A in formula (1a) is an O atom;

[0110] Step 2: A step of obtaining a compound represented by formula (I) in which A in formula (1a) is an S atom by reacting the compound represented by formula (I) in which A in formula (1a) is an O atom with a sulfiding agent.

[0111]

[0112] [In formula (II), n and R 11 Meanings the same as above.]

[0113]

[0114] [In formula (III), R 2 , L and m a represents the same meaning as above, and X represents a leaving group.]

[0115] The reaction of the compound represented by formula (II) (hereinafter also referred to as "compound (II)") and the compound represented by formula (III) (hereinafter also referred to as "compound (III)") in the first step can be carried out in the presence of a base, for example. Two or more bases may be used in combination. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium hydride, lithium aluminum hydride, sodium borohydride, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, and cesium bicarbonate; metal alkoxides such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium tert-butoxide, and potassium tert-butoxide; and organic bases such as ammonia, methylamine, dimethylamine, trimethylamine, triethylamine, diisopropylethylamine, triisopropylamine, DBU, DABCO, pyridine, 2,6-lutidine, 2,6-di-tert-butylpyridine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, and tetramethylammonium chloride. The amount of the base used is, for example, 0.01 to 10 mol, preferably 0.5 to 5 mol, relative to 1 mol of compound (II).

[0116] In formula (III), as the leaving group represented by X, halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms can be cited; alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, trifluoromethylsulfonyl, perfluoroethylsulfonyl, perfluoropropylsulfonyl, and perfluorobutylsulfonyl; arylsulfonyl groups such as phenylsulfonyl, p-toluenesulfonyl, p-fluorophenylsulfonyl, and pentafluorophenylsulfonyl. An example of compound (III) is an epihalohydrin compound (X is a halogen atom, L is a methylene group, and m a The amount of the compound (III) used is, for example, 0.01 to 20 mol, preferably 0.5 to 15 mol, relative to 1 mol of the compound (II). The first step may be carried out using two or more compounds (III).

[0117] The reaction of compound (II) and compound (III) is preferably carried out in a solvent. As the solvent, in addition to water, organic solvents such as ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, alcohols, glycol dimethyl ethers, esters, aliphatic nitriles, sulfoxides, and amides can also be mentioned. It is also possible to use two or more solvents in combination. As the organic solvent, specifically, the following solvents can be exemplified.

[0118] Ketones: acetone, methyl ethyl ketone, diethyl ketone, butyl methyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, 2-octanone, cyclopentanone, cyclohexanone, etc.

[0119] Aromatic hydrocarbons: benzene, toluene, xylene, mesitylene, naphthalene, anisole, nitrobenzene, aniline, tetralin, durene, etc.

[0120] Halogenated aromatic hydrocarbons: chlorobenzene, dichlorobenzene, chloronaphthalene, etc.

[0121] Aliphatic hydrocarbons: pentane, hexane, heptane, etc.

[0122] Halogenated aliphatic hydrocarbons: dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, etc.

[0123] Ethers: diethyl ether, diisopropyl ether, methyl tert-butyl ether, cyclopentyl methyl ether, diphenyl ether, dimethoxyethane, dioxane, etc.

[0124] Alcohols: methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, hexafluoroisopropanol, etc.

[0125] Glyme: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, etc.

[0126] Esters: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc.

[0127] Aliphatic nitriles: acetonitrile, etc.

[0128] Sulfoxides: dimethyl sulfoxide, sulfolane, etc.

[0129] Amides: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0130] The reaction temperature of compound (II) and compound (III) is, for example, -80 to 200° C., preferably 0 to 150° C. The compound represented by formula (I) obtained by the reaction, wherein A in formula (1a) is an O atom, may be isolated or may be subjected to the second step without isolation.

[0131] The reaction carried out in the second step is a reaction in which the oxygen atom of the epoxy group or the oxetanyl group of the compound represented by formula (I) in which A in formula (1a) is an O atom is replaced with a sulfur atom by a sulfiding agent, thereby forming a thiirane group (epithio group) or a thietane group. Examples of the sulfiding agent include thiourea, methylthiourea, dimethylthiourea, trimethylthiourea, tetramethylthiourea, tetraethylthiourea, ethylenethiourea, sodium thiocyanate, potassium thiocyanate, and the like. The amount of the sulfiding agent used is, for example, 0.01 to 20 mol, preferably 0.5 to 10 mol, relative to 1 mol of the compound represented by formula (I) in which A in formula (1a) is an O atom.

[0132] The reaction of the compound represented by formula (I) in which A in formula (1a) is an O atom and the sulfiding agent is preferably carried out in a solvent. As the solvent, the organic solvents exemplified above can be used. Two or more organic solvents can also be used in combination. The temperature of the reaction of the compound represented by formula (I) in which A in formula (1a) is an O atom and the sulfiding agent is, for example, -80 to 200°C, preferably 0 to 100°C.

[0133] In the second step, a polymerization inhibitor may be added to inhibit the polymerization of the compound represented by formula (I) in which A in the generated formula (1a) is an S atom. Examples of the polymerization inhibitor include acids and acid anhydrides. Specifically, examples include nitric acid, hydrochloric acid, perchloric acid, hypochlorous acid, chlorine dioxide, hydrofluoric acid, sulfuric acid, oleum, sulfonyl chloride, boric acid, arsenic acid, arsenous acid, pyroarsenic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphorus oxychloride, phosphorus oxybromide, phosphorus sulfide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, hydrocyanic acid, chromic acid, nitric anhydride, sulfuric anhydride, boric oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, silica gel, silica-alumina, aluminum chloride, zinc chloride and other inorganic acidic compounds; formic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, propionic acid, butyric acid, succinic acid, valeric acid, caproic acid, octanoic acid, cyclopentaneic acid, methyl mercaptopropionate, malonic acid, glutaric acid, hexanoic acid, Organic carboxylic acids such as diacid, cyclohexanecarboxylic acid, thiodipropionic acid, dithiodipropionic acid, acetic acid, maleic acid, benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, salicylic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, benzoylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, benzilic acid, α-naphthoic acid, β-naphthoic acid, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, trifluoroacetic anhydride, etc.; mono-, di- and tri-methyl phosphates, mono-, di- and tri-ethyl phosphates, mono-, di- and tri-isobutyl phosphates Phosphoric acids such as esters, mono-, di- and tri-butyl phosphates, mono-, di- and tri-lauryl phosphates, and phosphorous acids obtained by converting the phosphate esters thereof into phosphites; organic phosphorus compounds such as dialkyl dithiophosphoric acids represented by dimethyl dithiophosphoric acid; phenol, catechol, tert-butyl catechol, 2,6-di-tert-butylcresol, 2,6-di-tert-butylethylphenol, resorcinol, hydroquinone, phloroglucinol, pyrogallol, cresol, ethylphenol, butylphenol, nonylphenol, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, hydroxyphenylacetamide, hydroxyphenylacetic acid methyl ester, hydroxyphenylethyl ester, hydroxyphenylethanol, hydroxyphenylethylamine, hydroxybenzaldehyde, phenylphenol , bisphenol-A, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), bisphenol-F, bisphenol-S, α-naphthol, β-naphthol, aminophenol, chlorophenol, 2,4,6-trichlorophenol and other phenols; methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, p-toluenesulfonic acid, ethylbenzenesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid, p-phenolsulfonic acid, o-cresolsulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 4B acid, diaminostilbenesulfonic acid, biphenylsulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, perisulfonic acid, Laurentic acid, phenyl J acid and other sulfonic acids, etc., and multiple types can also be used in combination. The amount of the polymerization inhibitor to be used is, for example, 0.0001 to 1.0 mol, preferably 0.01 to 0.2 mol, based on 1 mol of the compound represented by the formula (I) in which A in the formula (1a) is an O atom.As the polymerization inhibitor, acetic acid, acetic anhydride, maleic acid and maleic anhydride are preferred.

[0134] In the second step, the stability over time of the compound represented by the formula (I) in which A is the S atom in the formula (1a) obtained by washing the product solution after the reaction with an acidic aqueous solution can be improved. As a specific example of the acid used in the acidic aqueous solution, nitric acid, hydrochloric acid, sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, succinic acid, maleic acid, etc. can be cited. They can be used alone or in combination with two or more. The aqueous solutions of these acids usually show effects below pH 6, but the more effective range is below pH 3. Preferably hydrochloric acid and sulfuric acid.

[0135] In addition, in the second step, in order to improve the stability of the compound represented by formula (I) in which A in formula (1a) is a S atom, a hydrogen sulfide adsorbent may be used. Examples of the hydrogen sulfide adsorbent include iron (III) hydroxide, zinc oxide, KNK-301 (zinc oxide adsorbent, manufactured by Kureha Oil & Fats Industries), NIONON 202A (iron oxide adsorbent, manufactured by Ibuki Masa Co., Ltd.), and LIMONIC (iron hydroxide adsorbent, manufactured by Japan LIMONIC). The hydrogen sulfide adsorbent may be added during the reaction in the second step, or may be used in the purification after the reaction.

[0136] <Resin (I)>

[0137] The resin (I) is not particularly limited as long as it has a refractive index of 1.60 or more at a wavelength of 550 nm and is a resin other than compound (I). The refractive index of the resin (I) at a wavelength of 550 nm may be 1.60 or more, 1.62 or more, 1.65 or more, or 1.67 or more. The refractive index at a wavelength of 550 nm may be, for example, 1.80 or less, or 1.78 or less.

[0138] Examples of the resin (I) include Novolac resins, resins having structural units derived from hydroxystyrene, and resins having structural units derived from at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "monomer (a)") (hereinafter sometimes referred to as "resin (B)").

[0139] Resin (I) is preferably a resin containing a polymerizable group selected from the group consisting of a (meth)acryloyl group, a mercapto group, a cyclic ether group having 2 to 4 carbon atoms, and a cyclic thioether group having 2 to 4 carbon atoms. By using such a resin, excellent curability can be exhibited. Resin (I) is preferably a resin containing a polymerizable group selected from the group consisting of a mercapto group, a cyclic ether group having 2 to 4 carbon atoms, and a cyclic thioether group having 2 to 4 carbon atoms. This is because, by using such a resin, it is easy to obtain a resin (I) having a refractive index of 1.60 or more at a wavelength of 550nm. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. Examples of the cyclic thioether group include a thiirane group and a thietane group.

[0140] Novolac resin is a resin obtained by condensing a phenol compound with an aldehyde in the presence of a catalyst. Examples of the phenol compound include phenol; o-cresol, m-cresol or p-cresol; 2,3-xylenol, 2,5-xylenol, 3,4-xylenol or 3,5-xylenol; 2,3,5-trimethylphenol; 2-tert-butylphenol, 3-tert-butylphenol or 4-tert-butylphenol; 2-tert-butyl-4-methylphenol or 2-tert-butyl-5-methylphenol; 2-dimethoxyphenol, 4-dimethoxyphenol or 5-methylresorcinol; 2-methoxyphenol, 3-methoxyphenol or 4-methoxyphenol; Phenol; 2,3-dimethoxyphenol, 2,5-dimethoxyphenol- or 3,5-dimethoxyphenol; 2-methoxyresorcinol; 4-tert-butylcatechol; 2-ethylphenol, 3-ethylphenol or 4-ethylphenol; 2,5-diethylphenol or 3,5-diethylphenol; 2,3,5-triethylphenol; 2-naphthol; 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene or 1,7-dihydroxynaphthalene; polyhydroxytriphenylmethane compounds obtained by condensation of xylenol and hydroxybenzaldehyde, etc. These phenol compounds may be used in combination of two or more. Among them, preferred phenol compounds are o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-tert-butyl-4-methylphenol, and 2-tert-butyl-5-methylphenol.

[0141] As aldehydes, for example, aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, acrolein or crotonaldehyde; alicyclic aldehydes such as cyclohexanealdehyde, cyclopentanealdehyde, furfural or furanyl acrolein; aromatic aldehydes such as benzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, 2,4-, 2,5-, 3,4- or 3,5-dimethylbenzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde or p-hydroxybenzaldehyde; aromatic aliphatic aldehydes such as phenylacetaldehyde or cinnamaldehyde. These aldehydes may also be used in combination of two or more. Among these aldehydes, formaldehyde is preferred from the perspective of being easily available in industry.

[0142] Examples of catalysts used in the condensation of phenol compounds and aldehydes include inorganic acids such as hydrochloric acid, sulfuric acid, perchloric acid or phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid, trichloroacetic acid or p-toluenesulfonic acid; divalent metal salts such as zinc acetate, zinc chloride or magnesium acetate, etc. These catalysts may be combined in two or more kinds. The amount of the catalyst used is usually 0.01 to 1 mole relative to 1 mole of the aldehyde.

[0143] The condensation reaction of the phenol compound and the aldehyde can be carried out, for example, by mixing the phenol compound and the aldehyde and reacting them at a temperature of 60 to 120° C. for 2 to 30 hours. The condensation reaction can also be carried out in the presence of a solvent. Examples of the solvent in the condensation reaction include methyl ethyl ketone, methyl isobutyl ketone, acetone, and the like. After the reaction is completed, for example, a water-insoluble solvent can be added to the reaction mixture as needed, and the reaction mixture can be washed with water and then concentrated to remove the Novolac resin.

[0144] The weight average molecular weight of the Novolac resin is usually 3,000 to 50,000, preferably 4,000 to 40,000, and more preferably 5,000 to 30,000. When the weight average molecular weight of the Novolac resin is within the above range, film thinning and residue remaining after development can be effectively prevented.

[0145] The resin having a polymerized unit derived from hydroxystyrene is typically polyvinylphenol, preferably poly-p-vinylphenol.

[0146] When the resin (I) is a Novolac resin, a preferred example is a resin represented by formula (A) (hereinafter also referred to as "resin (A)"). The resin (A) can provide a cured product having a high refractive index and can also exhibit excellent curability.

[0147]

[0148] [In formula (A),

[0149] R represents a monovalent hydrocarbon group. When there are multiple Rs, the multiple Rs may be the same or different.

[0150] n is the average value and represents a number greater than 1,

[0151] A represents an O atom or a S atom, and a plurality of A's may be the same or different.]

[0152] Formula (A) indicates that the group containing the A atom may be present at any position of the 1st to 8th positions of the naphthalene ring. In addition, the group R may be present at any position of the 2nd to 6th positions of the benzene ring.

[0153] When there are a plurality of Rs, R representing a monovalent hydrocarbon group may be independently selected from monovalent hydrocarbon groups such as a monovalent aliphatic chain hydrocarbon group which may have a substituent, a monovalent alicyclic hydrocarbon group which may have a substituent, a monovalent aromatic hydrocarbon group which may have a substituent, and a monovalent group (such as an aralkyl group) formed by a combination of these groups. 2 - can be replaced by -O-, -S-, -NR 1A -(R 1A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, -SO 2 -.

[0154] As the monovalent aliphatic chain hydrocarbon group, for example, a saturated or unsaturated aliphatic chain hydrocarbon group can be mentioned, and specifically, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc. can be mentioned. The monovalent aliphatic chain hydrocarbon group can be straight-chain or branched. The number of carbon atoms in the monovalent aliphatic chain hydrocarbon group is usually 1 to 20, preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and even more preferably 1 or 2.

[0155] Examples of the substituent which the monovalent aliphatic chain hydrocarbon group may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a hydroxyl group, an amino group, an acetyl group, and a cyano group.

[0156] Examples of the monovalent alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups, specifically, monocyclic alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl; and polycyclic alicyclic hydrocarbon groups such as bicyclo[1.1.0]butyl, tricyclo[2.2.1.0]heptyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2.]octyl, adamantyl, bicyclo[4.3.2]undecyl, and tricyclo[5.3.1.1]dodecyl. The number of carbon atoms in the monovalent alicyclic hydrocarbon group is usually 3 to 20, preferably 3 to 10, more preferably 3 to 6, and even more preferably 5 or 6.

[0157] Examples of the substituent that the monovalent alicyclic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, halogen atoms such as fluorine, chlorine, bromine and iodine atoms, hydroxyl, amino, acetyl and cyano groups.

[0158] The monovalent aromatic hydrocarbon group may be monocyclic or polycyclic, and examples thereof include phenyl, naphthyl, anthracenyl, fluorenyl, etc. The monovalent aromatic hydrocarbon group usually has 6 to 20 carbon atoms, and preferably 6 to 10 carbon atoms.

[0159] Examples of the substituent that the monovalent aromatic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, halogen atoms such as fluorine, chlorine, bromine and iodine atoms, hydroxyl, amino, acetyl and cyano groups.

[0160] R is preferably a monovalent aliphatic chain hydrocarbon group which may have a substituent, more preferably an alkyl group which may have a substituent, further preferably an alkyl group having 1 to 6 carbon atoms, further preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

[0161] R may be present at any of the 2-6 positions of the benzene ring, and is preferably present at the para position relative to the group containing the A atom.

[0162] n is an average value and represents a number greater than or equal to 1. Here, the resin (A) may be one resin represented by the formula (A) or a mixture of two or more resins represented by the formula (A). The "average value" mentioned above refers to the value of n (an integer greater than or equal to 1) possessed by the resin when the resin (A) is one resin represented by the formula (A), and refers to the average value of the values ​​of n possessed by the two or more resins when the resin (A) is a mixture of two or more resins represented by the formula (A). When the resin (A) is one resin represented by the formula (A), n is preferably any integer from 1 to 10, and more preferably any integer from 1 to 5. When the resin (A) is a mixture of two or more resins represented by the formula (A), n is preferably in the range of 1 to 10, and more preferably in the range of 1 to 5, as an average value. It should be noted that the two or more resins may also be resins having the same value of n but different other compositions.

[0163] A represents an O atom or an S atom, and a plurality of A's may be the same or different. The greater the ratio of the number of A's as S atoms to the total number of A's (hereinafter, also referred to as "S atom content ratio"), the greater the refractive index of the cured product. When at least one A is an S atom, it refers to an episulfide resin (A). From the viewpoint of improving the refractive index, the S atom content ratio of the resin (A) is preferably 0.5 or more, more preferably 0.6 or more, further preferably 0.7 or more, more preferably 0.8 or more, particularly preferably 0.9 or more, and most preferably 1.0. The S atom content ratio may also be less than 1.0. The average value here has the same meaning as above.

[0164] In formula (A), the bonding position of the group containing an A atom that is bonded to the naphthalene ring is not particularly limited, but is preferably the 1-position or 2-position of the naphthalene ring.

[0165] Examples of the resin represented by formula (A) include compounds represented by formula (Aa). R, n and A in formula (Ia) have the same meanings as above.

[0166]

[0167] As described above, resin (A) may also be a mixture of two or more resins represented by formula (A). As such a mixture, for example, a mixture of two or more compounds represented by formula (A) different from each other in any one or more of the S atom content ratio, the position of the group containing A atoms on the naphthalene ring, the type of R, the position of R on the benzene ring, and the value of n.

[0168] The weight average molecular weight Mw of the resin (A) is, for example, 500 to 10,000, or preferably 750 to 3,000, when calculated in terms of polystyrene by gel permeation chromatography (GPC).

[0169] The resin (B) has a structural unit derived from at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "monomer (a)"). The resin (B) may have a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b)"), or a structural unit derived from a monomer copolymerizable with the monomer (a) (however, different from the monomer (a) and the monomer (b), hereinafter sometimes referred to as "monomer (c)").

[0170] In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[0171] Examples of the monomer (a) include:

[0172] Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid;

[0173] Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

[0174] Bicyclic unsaturated compounds containing a carboxyl group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

[0175] Unsaturated dicarboxylic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;

[0176] Unsaturated mono-(meth)acryloyloxyalkyl) esters of polycarboxylic acids having a valence of 2 or more, such as mono-(meth)acryloyloxyethyl) succinate and mono-(meth)acryloyloxyethyl phthalate;

[0177] Unsaturated acrylic acid esters containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid; and the like.

[0178] Among them, acrylic acid, methacrylic acid, o-, m-, and p-vinylbenzoic acid, maleic anhydride, and the like are preferred from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an alkaline aqueous solution.

[0179] The monomer (b) is a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond.

[0180] The monomer (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0181] Examples of monomer (b) include a monomer having an ethylene oxide group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b1)"), a monomer having an oxetane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b2)"), and a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b3)").

[0182] Examples of the monomer (b1) include a monomer having a structure in which a straight-chain or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter sometimes referred to as "monomer (b1-1)") and a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter sometimes referred to as "monomer (b1-2)").

[0183] As the monomer (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferred.

[0184] Examples of the monomer (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl o-vinylbenzyl glycidyl ether, α-methyl m-vinylbenzyl glycidyl ether, α-methyl p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxy) 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tri(glycidyloxymethyl)styrene, 2,3,5-tri(glycidyloxymethyl)styrene, 2,3,6-tri(glycidyloxymethyl)styrene, 3,4,5-tri(glycidyloxymethyl)styrene, 2,4,6-tri(glycidyloxymethyl)styrene, and the like.

[0185] As monomers (b1-2), for example, vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer (registered trademark) M100; manufactured by Daicel Co., Ltd.), compounds represented by formula (BI) and compounds represented by formula (BII), etc.

[0186]

[0187] [In formula (BI) and formula (BII), R a and R b Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group.

[0188] X a and X b Independently of each other, they represent single bonds, *-R c -,*-R c -O-, *-R c -S- or *-R c -NH-.

[0189] R c It represents an alkanediyl group having 1 to 6 carbon atoms.

[0190] * indicates the bond to O. ]

[0191] Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

[0192] Examples of the alkyl group in which a hydrogen atom is replaced by a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.

[0193] As R a and R b , preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are mentioned, and more preferably, a hydrogen atom and a methyl group are mentioned.

[0194] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.

[0195] As X a and X b , preferably a single bond, a methylene group, an ethylene group, *-CH 2 -O-, *-CH 2 CH 2 -O-, more preferably a single bond, *-CH 2 CH 2 -O- (* indicates a bond with O).

[0196] Examples of the compound represented by formula (BI) include compounds represented by any one of formula (BI-1) to formula (BI-15). Among them, preferred are compounds represented by formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9), and formula (BI-11) to formula (BI-15), and more preferred are compounds represented by formula (BI-1), formula (BI-7), formula (BI-9), and formula (BI-15).

[0197]

[0198] As the compound represented by formula (BII), examples include compounds represented by any one of formulas (BII-1) to (BII-15), among which preferred examples include compounds represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9) and (BII-11) to (BII-15), and more preferred examples include compounds represented by formulas (BII-1), (BII-7), (BII-9) and (BII-15).

[0199]

[0200] The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination of two or more thereof. The compound represented by formula (BI) and the compound represented by formula (BII) may also be used in combination. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, their content ratio [compound represented by formula (BI): compound represented by formula (BII)] is preferably 5:95 to 95:5 on a molar basis, more preferably 10:90 to 90:10, and further preferably 20:80 to 80:20.

[0201] As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferred.

[0202] Examples of the monomer (b2) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyloxyethyloxetane, and 3-ethyl-3-(meth)acryloyloxyethyloxetane.

[0203] As the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuranyl group and a (meth)acryloyloxy group is more preferred.

[0204] Examples of the monomer (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0205] As monomer (b), monomer (b1) is preferred from the viewpoint of being able to further improve the reliability of the obtained cured product, such as heat resistance and chemical resistance. In addition, monomer (b1-2) is more preferred from the viewpoint of excellent storage stability of composition (I).

[0206] Examples of the monomer (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate, 2,6 ] decane-8-yl ester (in the technical field, it is commonly known as "dicyclopentanyl (meth)acrylate". In addition, it is sometimes called "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 2,6 ] decane-9-yl ester, (meth) acrylic acid tricyclo[5.2.1.0 2,6 ] decen-8-yl ester (in the technical field, it is commonly known as "dicyclopentenyl (meth)acrylate"), tricyclo[5.2.1.0 2,6 ] (meth)acrylates such as decen-9-yl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate and benzyl (meth)acrylate;

[0207] (Meth)acrylates containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

[0208] (Meth)acrylates containing halogen atoms such as 2,2,3,3,4,4,5,5-octafluoropentyl (meth)acrylate;

[0209] Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

[0210] bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene Bicyclic unsaturated compounds such as cyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene;

[0211] Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate and N-(9-acridinyl)maleimide;

[0212] Aromatic compounds containing vinyl groups, such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, N-vinylcarbazole and p-methoxystyrene; nitriles containing vinyl groups, such as (meth)acrylonitrile; halogenated hydrocarbons, such as vinyl chloride and vinylidene chloride; amides containing vinyl groups, such as (meth)acrylamide; esters, such as vinyl acetate; dienes, such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; and the like.

[0213] The content of the resin (I) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, further preferably 13 to 70% by mass, and further preferably 15 to 60% by mass relative to 100% by mass of the solid content of the composition (I). If the content of the resin (I) is within the above range, the refractive index of the cured product can be increased.

[0214] <Other ingredients>

[0215] As the above-mentioned other components contained in the composition (I), for example, a polymerizable compound other than the compound (I), a resin other than the resin (I) (hereinafter also referred to as "resin (II)"), a polymerization initiator, a polymerization initiation aid, a leveling agent, an antioxidant, a curing agent, etc. Examples of the curing agent include polycarboxylic acids, imidazole compounds, etc.

[0216] (1) Polymerizable compounds

[0217] The composition (I) may contain one or more polymerizable compounds in addition to the compound (I). By including a polymerizable compound in the composition (I), the viscosity or curability of the composition (I) can be adjusted, or the mechanical properties and / or optical properties of the obtained cured product and a molded product containing the same can be adjusted.

[0218] The polymerizable compound is not limited as long as it is a compound other than compound (I) and is a polymerizable compound. The polymerizable compound is a monomer that reacts by the action of heat or a polymerization initiator, and as such a monomer, for example, a compound having an ethylenically unsaturated bond can be cited, preferably a (meth)acrylic compound can be cited, and more preferably a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group can be cited.

[0219] Examples of the (meth)acrylic compound having two (meth)acryloyl groups include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bis(acryloyloxyethyl) ether of bisphenol A, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified neopentyl glycol di(meth)acrylate, ethylene oxide-modified neopentyl glycol di(meth)acrylate, and 3-methylpentanediol di(meth)acrylate.

[0220] Examples of the (meth)acrylic compound having three or more (meth)acryloyl groups include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, a reaction product of pentaerythritol tri(meth)acrylate and an acid anhydride, a reaction product of dipentaerythritol penta(meth)acrylate and an acid anhydride, and a reaction product of tripentaerythritol hepta(meth)acrylate and an acid anhydride. Caprolactone modified trimethylolpropane tri(meth)acrylate, caprolactone modified pentaerythritol tri(meth)acrylate, caprolactone modified tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, caprolactone modified tripentaerythritol tetra(meth)acrylate, caprolactone modified Tripentaerythritol penta(meth)acrylate, caprolactone-modified tripentaerythritol hexa(meth)acrylate, caprolactone-modified tripentaerythritol hepta(meth)acrylate, caprolactone-modified tripentaerythritol octa(meth)acrylate, a reaction product of caprolactone-modified pentaerythritol tri(meth)acrylate and an acid anhydride, a reaction product of caprolactone-modified dipentaerythritol penta(meth)acrylate and an acid anhydride, a reaction product of caprolactone-modified tripentaerythritol hepta(meth)acrylate and an acid anhydride, and the like.

[0221] As the (meth)acrylic compound, a (meth)acrylic compound having three or more (meth)acryloyl groups is preferred, and dipentaerythritol hexa(meth)acrylate is more preferred.

[0222] When the composition (I) contains a polymerizable compound, the content of the polymerizable compound is preferably 1 mass % or more, more preferably 2 mass % or more, and preferably 30 mass % or less, more preferably 20 mass % or less, relative to the total amount of the solid content of the composition (I).

[0223] (2) Resin (II)

[0224] The composition (I) may contain one or more resins (II). By making the composition (I) contain resin (II), it is possible to impart developability to the cured product of the composition (I), or to adjust the mechanical properties and / or optical properties of the cured product and a molded product containing the same. As resin (II), it is not limited as long as it is a resin other than resin (I), and thermoplastic resins and curable resins can be cited. The curable resin can be a photocurable resin cured by irradiation with active energy rays, or a thermosetting resin cured by heat.

[0225] As thermoplastic resin, for example, olefin resins such as polyethylene resin, polypropylene resin, polycycloolefin resin, (meth) acrylic resins such as poly (meth) acrylic ester resin, polystyrene resin, styrene-acrylonitrile resin, acrylonitrile-butadiene-styrene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyester resins such as liquid crystal polyester resin, polyacetal resin, polyamide resin, polycarbonate resin, polyurethane resin, polyphenylene sulfide resin, etc. can be enumerated. One or more of these resins can also be made into polymer blends or polymer alloys for use.

[0226] Examples of the curable resin include resins having a photopolymerizable group or a thermopolymerizable group, such as (meth)acrylic resins, epoxy resins, melamine resins, unsaturated polyester resins, phenolic resins, urea resins, alkyd resins, and polyimide resins.

[0227] (3) Polymerization initiator

[0228] The composition (I) may contain one or more polymerization initiators. As the polymerization initiator, there is no particular limitation as long as it can initiate the polymerization of the compound (I), for example, free radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, free radical and cationic polymerization initiators, etc. can be mentioned, and they can be appropriately selected and used. These polymerization initiators utilize at least one of active energy ray irradiation and heat to generate free radicals, acids or bases, so that free radical polymerization, cationic polymerization or anionic polymerization of the polymerizable compound can be carried out.

[0229] The polymerization initiator is preferably a polymerization initiator containing at least one selected from the group consisting of O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds, and more preferably a polymerization initiator containing an O-acyl oxime compound. These polymerization initiators have high sensitivity and tend to have a high transmittance in the visible light region.

[0230] The O-acyl oxime compound is a compound having a structure represented by formula (D1).

[0231]

[0232] Examples of the O-acyl oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, and N-acetoxy-1-[4-phenylsulfanylphenyl]octane-1-one-2-imine. -1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imide, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imide, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imide. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (both manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) can also be used.

[0233] The alkylphenone compound is a compound having a structure represented by formula (D2-1) or a structure represented by formula (D2-2). In these structures, the benzene ring may have a substituent.

[0234]

[0235] As the compound having the structure represented by formula (D2-1), for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one can be mentioned. Commercially available products such as Irgacure (registered trademark) 369, 907 and 379 (all manufactured by BASF (Strain)) can also be used. In addition, polymerization initiators having a group capable of causing chain transfer as described in Japanese Patent Application Laid-Open No. 2002-544205 can also be used. Examples of compounds having a structure represented by formula (D2-2) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzil dimethyl ketal. From the perspective of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (D2-1).

[0236] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine.

[0237] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure 819 (manufactured by BASF Japan Co., Ltd.) may also be used.

[0238] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-Open No. 6-75372 and Japanese Patent Application Laid-Open No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with alkoxycarbonyl groups (for example, see Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazoles, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazoles (for example, see Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with alkoxycarbonyl groups (for example, see Japanese Patent Publication No. 7-10913, etc.).

[0239] In addition, examples of polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis (tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, and titanocene compounds, etc. These may be used in combination with the polymerization initiator aid (particularly amine compounds) described later.

[0240] As the polymerization initiator, an acid generator may also be used. Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl toluenesulfonate, and benzoin toluenesulfonate.

[0241] When the composition (I) contains a polymerizable compound and a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 1 to 8 parts by mass relative to 100 parts by mass of the total content of the resin and the polymerizable compound. If the content of the polymerization initiator is within the above range, there is a tendency for the visible light transmittance of the obtained cured product to be high.

[0242] (4) Polymerization initiator

[0243] The polymerization initiation aid is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound which is polymerized by the polymerization initiator together with the polymerization initiator.

[0244] Examples of the polymerization initiation aid include thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0245] Examples of the thiazoline compound include compounds represented by formula (H1-1) to formula (H1-3), and compounds described in JP-A-2008-65319.

[0246]

[0247] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone. Among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may also be used.

[0248] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

[0249] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0250] Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0251] When the composition (I) contains a polymerizable compound, a polymerization initiator and a polymerization initiation aid, the content of the polymerization initiation aid is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 10 parts by mass, relative to 100 parts by mass of the total content of the resin (I) and the polymerizable compound. If the amount of the polymerization initiation aid is within the above range, when a cured product is formed, the sensitivity tends to be higher.

[0252] (5) Leveling agent

[0253] Examples of the leveling agent include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms, etc. These may have a polymerizable group in a side chain.

[0254] Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specific examples include TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, TORAY SILICONE SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Materials Japan Co., Ltd.).

[0255] Examples of the fluorine-based surfactant include surfactants having a fluorine-carbon chain in the molecule. Specifically, examples include FLOURAD (registered trademark) FC430, FLOURAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFACE (registered trademark) F142D, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACE F183, MEGAFACE F554, MEGAFACE R30, MEGAFACE RS-718-K (manufactured by DIC Co., Ltd.), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), SURFLON (registered trademark) S381, SURFLON S382, SURFLON SC101, SURFLON SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Laboratories, Ltd.), etc.

[0256] Examples of the above-mentioned silicone surfactant having fluorine atoms include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, and more specifically, MEGAFACE (registered trademark) R08, MEGAFACE BL20, MEGAFACE F475, MEGAFACE F477, and MEGAFACE F443 (manufactured by DIC Corporation).

[0257] When the leveling agent is contained, the content rate is preferably 0.001 mass % to 0.2 mass % based on the total amount of the resin composition, more preferably 0.002 mass % to 0.1 mass %, further preferably 0.005 mass % to 0.07 mass %.

[0258] (6) Antioxidants

[0259] Examples of the antioxidant include phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. Among them, phenolic antioxidants are preferred because the resulting film is less colored.

[0260] Examples of the phenolic antioxidant include 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10- -tetraoxaspiro[5.5]undecane, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-butylenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6-tert-butyl-4-methylphenol), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H, 3H,5H)-trione, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[ d,f][1,3,2]dioxaphosphine. As the above-mentioned phenolic antioxidant, a commercially available product may also be used. Examples of commercially available phenolic antioxidants include Sumilizer (registered trademark) BHT, GM, GS, GP (all of which are manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX (registered trademark) 1010, 1076, 1330, 3114 (all of which are manufactured by BASF Co., Ltd.).

[0261] As the sulfur-based antioxidant, for example, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate) can be cited. As the aforementioned sulfur-based antioxidant, commercially available products can also be used. As commercially available sulfur-based antioxidants, for example, Sumilizer (registered trademark) TPL-R, TP-D (all of the above are manufactured by Sumitomo Chemical Co., Ltd.) can be cited.

[0262] As the phosphorus-based antioxidant, for example, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris(nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite can be cited. As the aforementioned phosphorus-based antioxidant, commercially available products can also be used. As commercially available phosphorus-based antioxidants, for example, IRGAFOS (registered trademark) 168, 12, 38 (all of the above are manufactured by BASF (KK)), ADK STAB 329K, ADK STAB PEP36 (all of the above are manufactured by ADEKA (KK)).

[0263] As the amine antioxidant, for example, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-diisopropyl-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine can be cited. As the aforementioned amine antioxidant, commercially available products can also be used. As commercially available amine antioxidants, for example, Sumilizer (registered trademark) BPA, BPA-M1, 4ML (all of the above are manufactured by Sumitomo Chemical Co., Ltd.) can be cited.

[0264] When the composition (I) contains an antioxidant, the content is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the total content of the resin and the polymerizable compound. If the content of the antioxidant is within the above range, the heat resistance and pencil hardness of the obtained cured product tend to be excellent.

[0265] (7) Curing agent

[0266] <Polycarboxylic Acid>

[0267] As a curing agent, a polycarboxylic acid can be used. The polycarboxylic acid is at least one compound selected from the group consisting of a polycarboxylic anhydride and a polycarboxylic acid. The so-called polycarboxylic acid is a compound having two or more carboxyl groups, and the so-called polycarboxylic anhydride is an acid anhydride of a polycarboxylic acid. The molecular weight of the polycarboxylic acid is preferably 3000 or less, and more preferably 1000 or less.

[0268] Examples of the polycarboxylic acid anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecylsuccinic anhydride, 2-(2-oct-3-enyl)succinic anhydride, 2-(2,4,6-trimethylnon-3-enyl)succinic anhydride, tricarboxylic anhydride, 1,2,3,4-butanetetracarboxylic anhydride and the like; and chain polycarboxylic anhydrides such as 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, norbornene dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2. alicyclic polycarboxylic acid anhydrides such as 2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, cyclopentanetetracarboxylic anhydride, etc.; aromatic polycarboxylic acid anhydrides such as phthalic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic anhydride, ethylene glycol bis(anhydrotrimellitic ester), glycerol tris(anhydrotrimellitic ester), glycerol bis(anhydrotrimellitic ester) monoacetate, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)naphtho[1,2-c]furan-1,3-dione, etc. Commercially available products such as Adeka Hardener (registered trademark)-EH-700 (trade name (hereinafter the same), manufactured by ADEKA Co., Ltd.), RIKACID (registered trademark)-HH, RIKACID-TH, RIKACID-MH, RIKACID MH-700 (manufactured by Shin Nippon Rika Co., Ltd.), EPIKINI 126, EPIKINI YH-306, and EPIKINIDX-126 (manufactured by Yuka Shell EPOXY Co., Ltd.) can also be used.

[0269] Examples of the aforementioned polycarboxylic acid include chain polycarboxylic acids such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and polycarboxylic acids derived from chain polycarboxylic acid anhydrides; alicyclic polycarboxylic acids such as cyclohexanedicarboxylic acid and polycarboxylic acids derived from alicyclic polycarboxylic acid anhydrides; aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and polycarboxylic acids derived from aromatic polycarboxylic acid anhydrides; and the like.

[0270] Among them, chain carboxylic acid anhydrides and alicyclic polycarboxylic acid anhydrides are preferred, and alicyclic polycarboxylic acid anhydrides are more preferred, because the resulting film has excellent heat resistance and, in particular, the transparency in the visible light region is less likely to decrease.

[0271] When the composition (I) contains a polycarboxylic acid, the content is preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and even more preferably 2 to 15 parts by mass relative to 100 parts by mass of the total content of the resin and the polymerizable compound. When the content of the polycarboxylic acid is within the above range, the obtained film has excellent heat resistance and adhesion.

[0272] <Imidazole compounds>

[0273] As the curing agent, an imidazole compound can be used. The imidazole compound is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include compounds known as epoxy curing agents. Among them, the compound represented by formula (G2-1) is preferred.

[0274]

[0275] [In formula (G2-1), R 31 It represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, a benzyl group, or a cyanoalkyl group having 2 to 5 carbon atoms.

[0276] R 32 ~R 34 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group, or an acyl group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the alkyl group and the phenyl group may be substituted by a hydroxyl group.]

[0277] Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isobutyl, butyl, tert-butyl, hexyl, heptyl, octyl, nonyl, decyl, heptadecyl and undecyl.

[0278] Examples of the cyanoalkyl group having 2 to 5 carbon atoms include a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group, and a cyanopentyl group.

[0279] Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0280] Examples of the acyl group having 1 to 20 carbon atoms include formyl, acetyl, propionyl, isobutyryl, valeryl, isovaleryl, pivaloyl, lauroyl, myristoyl and stearoyl.

[0281] Examples of the imidazole compound include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2-hydroxymethylimidazole, 1-benzyl-4-methylimidazole, imidazole, 1-benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2-(p-hydroxyphenyl)imidazole, 1-cyanomethyl-2-methylimidazole, 1-(2-cyanoethyl)-2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl-4-methylimidazole, 1-cyanomethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole. Among them, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole are preferred.

[0282] When the composition (I) contains an imidazole compound, the content thereof is preferably 0.1 to 25 parts by mass, more preferably 0.2 to 15 parts by mass, and further preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total content of the resin and the polymerizable compound. If the content of the imidazole compound is within the above range, the obtained cured product tends to have excellent transparency in the visible light region.

[0283] (8) Solvent

[0284] Composition (I) contains solvent. As solvent, it is not particularly limited, and the solvent commonly used in this field can be cited. For example, ester solvent (a solvent containing -COO- and not containing -O- in the molecule), ether solvent (a solvent containing -O- and not containing -COO- in the molecule), ether ester solvent (a solvent containing -COO- and -O- in the molecule), ketone solvent (a solvent containing -CO- and not containing -COO- in the molecule), alcohol solvent (a solvent containing OH and not containing -O-, -CO- and -COO- in the molecule), aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc. can be cited.

[0285] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0286] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, and methyl anisole.

[0287] Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0288] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0289] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0290] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene. Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0291] Among the above-mentioned solvents, organic solvents having a boiling point of 100° C. to 200° C. at 1 atm are preferred from the viewpoint of coating properties and drying properties. As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol ethyl methyl ether, cyclohexanone, methoxybutanol, and methoxybutyl acetate are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, methoxybutanol, and methoxybutyl acetate are more preferred.

[0292] The content of the solvent in the composition (I) is preferably 60 to 95% by mass, more preferably 70 to 95% by mass, relative to the total amount of the composition (I). In other words, the solid content of the composition (I) of the present invention is preferably 5 to 40% by mass, more preferably 5 to 30% by mass.

[0293] (9) Other ingredients

[0294] The composition (I) may contain additives known in the technical field such as a filler, other polymer compounds, a UV absorber, a chain transfer agent, and an adhesion promoter, as required.

[0295] (10) Method for producing composition (I)

[0296] The composition (I) can be prepared by mixing the compound (I) and the resin (I), and, if necessary, a solvent, a polymerizable compound, a polymerization initiator, a polymerization initiation aid, a leveling agent, an antioxidant, a curing agent and other components by a known method. After mixing, the mixture is preferably filtered using a filter having a pore size of about 0.05 to 1.0 μm.

[0297] <Solidified and molded products>

[0298] The present invention provides a cured product of composition (I), and a molded product comprising the cured product. Composition (I) is excellent in curability, and therefore, is suitable as a curable material for making a cured product or a molded product comprising the cured product. The cured product can be obtained by curing composition (I) by utilizing at least any one of active energy ray irradiation and heat. The shape of the molded product comprising the cured product is not particularly limited, and can be any shape corresponding to the purposes of the molded product, such as film, plate, lens, powder, granular, non-spherical particle, broken particle, porous, blocky continuum, fiber, tubular, hollow filament, etc.

[0299] The method for obtaining a molded product from the composition (I) is not particularly limited, and examples thereof include a method of forming a film on a substrate and then molding by etching or the like, an injection molding method, and a cast polymerization molding method.

[0300] In the cast polymerization molding method, for example, the composition (I) is injected into a molding die, degassed as needed, and then cured by heating in an oven, etc., and the obtained molded product is taken out. The taken out molded product may be further irradiated with active energy rays for additional curing.

[0301] In the case of forming a film as a molded object on a substrate, composition (I) can be applied to a substrate, dried as required to form a coating layer, and the coating layer is cured to obtain a molded object as a cured film. The molded object can also be a patterned cured film. Patterning can be performed by using methods such as photolithography, inkjet, and printing methods to obtain a patterned cured film. The patterning method is preferably photolithography. Photolithography is the following method: composition (I) is applied to a substrate, dried as required to form a coating layer, and the coating layer is exposed across a photomask, followed by development.

[0302] As the substrate, quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass having a surface coated with silicon dioxide, resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, and substrates having thin films of aluminum, silver, silver / copper / palladium alloy formed on the above substrates can be used. Examples of the method for applying the composition (I) to the substrate include spin coating, slit coating, and slit and spin coating.

[0303] As the light source used in the exposure, a light source that generates light with a wavelength of 250 nm or more and 450 nm or less is preferred. For example, a bandpass filter can be used to selectively extract light near 436 nm, near 408 nm, or near 365 nm from the light of the wavelength according to the absorption wavelength of the photopolymerization initiator. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, etc. can be cited as the light source. Heating (pre-development baking) can also be performed after the pattern is exposed and before development.

[0304] As the developer used in the development, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide, and organic solvents can be cited. As the organic solvent, organic solvents such as ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, alcohols, glycol dimethyl ethers, esters, aliphatic nitriles, sulfoxides, and amides can be cited. It is also possible to use two or more solvents in combination. The developer may contain a surfactant. The development method may be any method such as a spin-on immersion method, an immersion method, and a spray method. The patterned film obtained by the development may also be further heated (post-baked).

[0305] The cured product or the molded product containing the same is formed by the composition (I), and therefore, can show a high refractive index. In addition, their refractive index can be controlled to a desired refractive index by adjusting the composition of the composition (I). The refractive index of the cured product or the molded product containing the same at a wavelength of 550 nm can be 1.70 or more, 1.72 or more, and 1.75 or more. The refractive index at a wavelength of 550 nm is, for example, 1.80 or less, or 1.78 or less.

[0306] [use]

[0307] According to the present invention, a cured product or a molded product having a high refractive index, or a cured product or a molded product having a desired refractive index can be obtained. Examples of uses of the cured or molded product include glass substitutes and surface coating materials thereof; coating materials for window glass, lighting glass, and light source protection glass of residences, facilities, transportation equipment, etc.; window films of residences, facilities, transportation equipment, etc.; interior and exterior decorative materials and interior and exterior decorative coatings of residences, facilities, transportation equipment, etc., and coating films formed using the coatings; alkyd resin spray paints and coating films formed using the coatings; acrylic spray paints and coating films formed using the coatings; components for light sources emitting ultraviolet light such as fluorescent lamps and mercury lamps; materials for blocking electromagnetic waves generated from precision machinery, components for electronic and electrical equipment, and various displays; containers or packaging materials for food, chemicals, and pharmaceuticals; sheets or films for bottles, boxes, blisters, cups, special packaging, laser disc coatings, and agricultural industry; anti-fading agents for printed materials, dyed materials, dyes, pigments, etc.; protective films for polymer supports (e.g., for plastic components such as machinery and automobile parts); printed material protective layers; inkjet media coatings; laminated matte materials; optical light sheets (optical light sheets); lightfilm); safety glass / windshield interlayer; electrochromic / photochromic applications; overlaminate film; solar heat control film; cosmetics such as sunscreen, shampoo, hair dye (rinse), and hair treatment; fiber products and fibers for clothing such as sportswear, stockings, and hats; home interior decorations such as curtains, carpets, and wallpaper; medical devices such as plastic lenses, contact lenses, and artificial eyes; optical products such as optical filters, backlight display films, prisms, lenses (for example, eyeglass lenses, camera lenses, and microlenses and pickup lenses described below), mirrors, and photographic materials; stationery such as mold films, transfer stickers, anti-graffiti films, tapes, and inks; signboards, markers, etc. and their surface coating materials; substrates used in optical devices, etc.; optical waveguides; holograms; LED sealing materials; etc.

[0308] The molded article can be suitably used as an optical product, i.e., a lens, used in an optical device. Examples of optical devices include solid-state imaging devices and display devices. In solid-state imaging devices, lenses are used to improve the efficiency of focusing light into each photoelectric conversion element. In addition, in display devices, lenses are used to improve the efficiency of extracting light from pixels. The lens may be a microlens. As a display device, it can be suitably used in a liquid crystal display device, an organic EL display device, and the like.

[0309] Example

[0310] The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the Examples, % and parts indicating the content or the amount used are based on mass unless otherwise specified.

[0311] [Synthesis Example of Compound (I)]

[0312] <Synthesis Example 1: Synthesis of a compound represented by formula (Ia-21)>

[0313] Synthesis of the compound represented by formula (Ia-11)

[0314]

[0315] A four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, and 30 parts of the compound represented by formula (IIa-1) (1,6-naphthalenedithiol), 165 parts of acetone, 45 parts of pure water, and 139 parts of the compound represented by formula (III-1) (epichlorohydrin) were added to the above flask and stirred in an ice bath for 15 minutes. Next, 15 parts of sodium hydroxide, 66 parts of acetone, and 203 parts of pure water were added to another flask, and after completely dissolving them, they were added dropwise to the above four-necked flask over 1 hour. After the addition, the temperature was raised to 30°C and stirred at 30°C for 2 hours. The obtained mixture was purified to obtain 46 parts of the compound represented by formula (Ia-11).

[0316] LC-MS determination and 1 H-NMR analysis confirmed the formation of the compound represented by formula (Ia-11).

[0317] 1 H-NMR (deuterated chloroform) δ: 8.37-8.39 (1H), 7.85 (1H), 7.39-7.70 (4H), 3.08-3.29 (5H), 2.94-2.98 (1H), 2.57-2.81 (3H), 2.39-2.41 (1H)

[0318] LC-MS: [M+H] + =305.5

[0319] (2) Synthesis of the compound represented by formula (Ia-21)

[0320]

[0321] A four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, 3 parts of the compound represented by formula (Ia-11), 30 parts of methanol, 30 parts of toluene, 0.05 parts of acetic anhydride, and 3.8 parts of thiourea were added to the flask, and stirred at room temperature for 24 hours. The obtained mixture was purified to obtain 2.5 parts of the compound represented by formula (Ia-21).

[0322] LC-MS determination and 1 H-NMR analysis confirmed the formation of the compound represented by formula (Ia-21).

[0323] 1 H-NMR (deuterated chloroform) δ: 8.39-8.43 (1H), 7.86 (1H), 7.40-7.74 (4H), 3.40-3.53 (2H), 3.04-3.18 (2H), 2.78-2.96 (2H), 2.47-2.49 (1H), 2.35-2.36 (1H), 2.14-2.16 (1H), 1.93-1.94 (1H)

[0324] LC-MS: [M+H] + =337.5

[0325] <Synthesis Example 2: Synthesis of a compound represented by formula (Ic-21)>

[0326] (1) Synthesis of the compound represented by formula (Ic-11)

[0327]

[0328] A four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, and 15 parts of the compound represented by formula (IIc-1) (2,7-naphthalenedithiol), 83 parts of acetone, 23 parts of pure water, and 69 parts of the compound represented by formula (III-1) (epichlorohydrin) were added to the above flask and stirred in an ice bath for 15 minutes. Next, 7.5 parts of sodium hydroxide, 33 parts of acetone, and 101 parts of pure water were added to another flask, and after being completely dissolved, they were added dropwise to the above four-necked flask over 1 hour. After the addition, the temperature was raised to 65°C using an oil bath and stirred at 65°C for 1 hour. The resulting mixture was purified to obtain 24 parts of the compound represented by formula (Ic-11).

[0329] LC-MS determination and 1 H-NMR analysis confirmed the formation of the compound represented by formula (Ic-11).

[0330] 1H-NMR (deuterated chloroform) δ: 7.70-7.76 (4H), 7.43-7.45 (2H), 3.21-3.27 (4H), 3.05-3.11 (2H), 2.78-2.80 (2H), 2.57-2.58 (2H)

[0331] LC-MS: [M+H] + =305.5

[0332] (2) Synthesis of the compound represented by formula (Ic-21)

[0333]

[0334] A four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, 20 parts of the compound represented by formula (Ic-11), 320 parts of methanol, 80 parts of dichloromethane, and 25 parts of thiourea were added to the flask, and stirred at room temperature for 24 hours. The resulting mixture was purified to obtain 18.1 parts of the compound represented by formula (Ic-21).

[0335] LC-MS determination and 1 H-NMR analysis confirmed the formation of the compound represented by formula (Ic-21).

[0336] 1 H-NMR (deuterated chloroform) δ: 7.73-7.79 (4H), 7.46-7.48 (2H), 3.52-3.57 (2H), 3.14-3.18 (2H), 2.90-2.96 (2H), 2.49-2.51 (2H), 2.15-2.17 (2H)

[0337] LC-MS: [M+H] + =337.5

[0338] [Synthesis Example of Resin (I)]

[0339] <Synthesis Example 3: Synthesis of Resin Represented by Formula (Aa-2)>

[0340]

[0341] [In the formula, A and n have the same meanings as above.]

[0342] A four-necked flask equipped with a Dimroth condenser and a thermometer was set to a nitrogen atmosphere, and 20 parts of a resin represented by formula (Aa-1) (naphthol-cresol Novolac type epoxy resin "NC-7000L" manufactured by Nippon Kayaku Co., Ltd.), 320 parts of dichloromethane, 80 parts of methanol, and 33 parts of thiourea were added to the flask and stirred at room temperature for 72 hours. The obtained mixture was purified to obtain 14 parts of a resin represented by formula (Aa-2).

[0343] conduct 1 H-NMR analysis confirmed the formation of the resin represented by formula (Aa-2). The peak at 2.56 to 2.96 ppm derived from the epoxy group completely disappeared, and the formation of the peak derived from thiirane was confirmed again at 2.40 to 2.65 ppm.

[0344] According to the above 1 H-NMR analysis was performed to determine the ratio of the number of A atoms as S atoms to the total number of A atoms (S atom content ratio), and the average value was 1.0. In addition, according to GPC, the weight average molecular weight Mw of the resin represented by formula (Aa-2) was 1500, and Mn was 600.

[0345] Device: K2479 (manufactured by Shimadzu Corporation)

[0346] Column: SHIMADZU Shim-pack GPC-80M

[0347] Column temperature: 40°C

[0348] Solvent: Tetrahydrofuran

[0349] Flow rate: 1.0mL / min

[0350] Detector: RI

[0351] Calibration standard substances: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH Corporation)

[0352] The refractive index at a wavelength of 550 nm of the resin represented by the formula (Aa-1) and the formula (Aa-2) was calculated according to the following procedure.

[0353] 100 parts by mass of the resin represented by formula (Aa-1) or the resin represented by formula (Aa-2), 310 parts by mass of cyclopentanone as a solvent are loaded into a flask and stirred to obtain a liquid composition. The composition is transparent when viewed visually, confirming that the ingredients have been uniformly dissolved. About 3cc of the composition prepared above is added dropwise to alkali-free glass (Eagle XG thickness 0.7mm, Corning company system), and a spin coater (MS-B100, MIKASA system) is used to spin-coat at 1000rpm and 20 seconds to form a coating layer. The alkali-free glass plate formed with a coating layer is heated for 5 minutes at 60°C, the solvent is dried, and an alkali-free glass having a coating film without a solvent is obtained. Using a stylus film thickness meter (DekTak XT, Bruker system), the film thickness of the coating film on the alkali-free glass is measured, and the result is 1.5μm.

[0354] For the alkali-free glass on which the coating film is formed, the transmission spectrum and the reflection spectrum were measured with respect to the reflection spectrum at wavelengths of 300 nm to 800 nm using a visible ultraviolet spectrophotometer (V-650, JASCO Corporation) with an integrating sphere unit (ISV-922, JASCO Corporation). The refractive index of the coating film at a wavelength of 550 nm was calculated based on the Fresnel formula (Hecht Optics I Original Works, 5th Edition, Maruzen Publishing, 2018, p.209-p.226) from the value of a wavelength of 550 nm in the true reflection spectrum obtained by subtracting and smoothing the increase and decrease caused by interference in the reflection spectrum from the transmission spectrum and the reflection spectrum and the refractive index of the alkali-free glass (EagleXG, Corning).

[0355] The refractive indices of the resins represented by Formula (Aa-1) and Formula (Aa-2) at a wavelength of 550 nm are 1.63 and 1.66, respectively.

[0356] [Example 1: Preparation of composition]

[0357] 70 parts by mass of the compound represented by formula (Ia-21) obtained in Synthesis Example 1, 30 parts by mass of the resin represented by formula (Aa-2), 5 parts by mass of polymerization initiator A, and 310 parts by mass of cyclopentanone as a solvent were placed in a flask and stirred to obtain a liquid composition. The composition was transparent when visually observed, confirming that the ingredients were uniformly dissolved.

[0358] [Examples 2 to 6, Comparative Examples 1 to 3]

[0359] Liquid compositions were obtained in the same manner as in Example 1 except that the types of ingredients and their addition amounts in the composition were as shown in Table 1. The compositions of Examples 2 to 6 and Comparative Examples 1 to 3 were visually transparent, and it was confirmed that the ingredients were uniformly dissolved.

[0360] The details of the abbreviations of the blending components shown in Table 1 are as follows.

[0361] [1] (Ia-21): A compound represented by formula (Ia-21)

[0362] [2] (Ic-21): A compound represented by formula (Ic-21)

[0363] [3] (IB): A compound represented by formula (IB)

[0364]

[0365] [4] (Y1): A compound represented by the formula (Y1) (1,6-bis(glycidyloxy)naphthalene, "EPICLON HP-4032D" manufactured by DIC Corporation)

[0366]

[0367] [5] (Aa-1): Resin represented by formula (Aa-1) (naphthol-cresol Novolac type epoxy resin "NC-7000L" manufactured by Nippon Kayaku Co., Ltd.)

[0368] [6] (Aa-2): Resin represented by formula (Aa-2)

[0369] [7] Polymerization initiator A: Sulfonium salt type photocationic polymerization initiator ("VC-1S" manufactured by San-Apro Co., Ltd.)

[0370] [8] Polymerization initiator B: Sulfonium salt type photocationic polymerization initiator ("VC-1FG" manufactured by San-Apro Co., Ltd.)

[0371] [9] Polymerization initiator C: Onium salt type thermal cationic polymerization initiator ("TA-100" manufactured by San-Apro Co., Ltd.)

[0372] [Evaluation test]

[0373] (1) Refractive index of cured product

[0374] About 3 cc of the composition prepared above was dropped onto an alkali-free glass (Eagle XG thickness 0.7 mm, manufactured by Corning) and spin-coated at 1000 rpm for 20 seconds using a spin coater (MS-B100, manufactured by MIKASA) to form a coating layer. The alkali-free glass plate with the coating layer was heated at 60°C for 2 minutes. Next, a high-pressure mercury lamp proximity UV exposure device (UV-3300SC, manufactured by USHIO) was used to expose the glass in an atmospheric atmosphere at 1000 mJ / cm 2The alkali-free glass plate having the coating layer formed thereon was exposed to an irradiation energy of 1000 nm. Then, the exposed alkali-free glass plate having the coating layer formed thereon was heated at 120° C. for 5 minutes to obtain an alkali-free glass having a cured film formed thereon. The film thickness of the cured film on the alkali-free glass was measured using a stylus film thickness meter (DekTak XT, manufactured by Bruker) and the result was 1.5 μm.

[0375] For the alkali-free glass formed with a cured film, the transmission spectrum and reflection spectrum were measured using a visible ultraviolet spectrophotometer (V-650, JASCO) with an integrating sphere unit (ISV-922, JASCO). According to the value of the wavelength of 550nm in the real reflection spectrum obtained by subtracting the increase and decrease caused by the interference of the reflection spectrum from the transmission spectrum and the reflection spectrum and smoothing, and the refractive index of the alkali-free glass (EagleXG, Corning), the refractive index of the cured film at a wavelength of 550nm was calculated based on the Fresnel formula (Hecht Optics I Original 5th Edition, Maruzen Publishing, 2018, p.209-p.226). The results are shown in Table 1.

[0376] (2) Curing

[0377] About 3cc of the composition prepared above was dropped onto an alkali-free glass (Eagle XG thickness 0.7mm, manufactured by Corning), and spin-coated using a spin coater (MS-B100, manufactured by MIKASA) at 1000rpm for 20 seconds to form a coating layer. The alkali-free glass plate having a coating layer was heated at 60°C for 2 minutes. Next, a high-pressure mercury lamp proximity UV exposure device (UV-3300SC, manufactured by USHIO) was used for the alkali-free glass plate having a coating layer formed thereon, and the irradiation energy shown in Table 1 was used for exposure in an atmospheric atmosphere. Next, the alkali-free glass plate having a coating layer formed thereon after exposure was heated at the post-baking temperature and time shown in Table 1 to obtain an alkali-free glass having a cured film formed thereon. The film thickness of the cured film on the alkali-free glass was measured using a stylus film thickness meter (DekTak XT, manufactured by Bruker), and the result was 1.5μm.

[0378] The obtained cured film was evaluated for curability according to the following evaluation criteria. The results are shown in Table 1. For curability, the alkali-free glass having the cured film formed thereon was immersed in acetone at 23° C. for 10 minutes, and the film thickness retention rate before and after the immersion (film thickness retention rate = film thickness after immersion ÷ film thickness before immersion) was used for evaluation.

[0379] A: Film thickness retention rate is 90% or more and 100% or less

[0380] B: Film thickness retention rate is 80% or more and less than 90%

[0381] C: Film thickness retention rate is less than 80%

[0382] [Table 1]

[0383]

Claims

1. A composition comprising a compound represented by formula (I) and a resin having a refractive index of 1.60 or more at a wavelength of 550 nm, In formula (I), n represents any integer from 0 to 6, L represents a single bond or a divalent group. Multiple Ls may be the same or different. R 11 represents a monovalent substituent, R 11 When there are multiple R 11 Can be the same or different, R 12 A plurality of R is selected from the group consisting of a hydrogen atom, formula (1a), and formula (1b). 12 Can be the same or different, In formula (1a), A represents an O atom or a S atom. In formula (I), when there are multiple A's, the multiple A's may be the same or different. m a represents 0 or 1, in formula (I), m a When there are multiple m a Can be the same or different, R 2 represents a hydrogen atom or a monovalent substituent, R 2 When there are multiple R 2 Can be the same or different, * indicates the connection bond with L, In formula (1b), R 13 represents a monovalent substituent, R 13 When there are multiple R 13 Can be the same or different, * indicates a bond to L.

2. The composition according to claim 1, wherein The resin includes a polymerizable group selected from the group consisting of a (meth)acryloyl group, a mercapto group, a cyclic ether group having 2 to 4 carbon atoms, and a cyclic thioether group having 2 to 4 carbon atoms.

3. The composition according to claim 1, wherein The resin is a resin represented by formula (A), In formula (A), R represents a monovalent hydrocarbon group. When there are multiple Rs, the multiple Rs may be the same or different. n is the average value and represents a number greater than 1, A represents an O atom or a S atom, and plural A's may be the same or different.

4. The composition of claim 1, further comprising a polymerization initiator.

5. The composition according to claim 1, wherein The compound represented by formula (I) includes a plurality of R 12 A compound represented by formula (1a).

6. A cured product of the composition according to claim 1.

7. A display device comprising the cured product according to claim 5. 8 . A solid-state imaging device comprising the cured product according to claim 7 .

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