Compound, method for producing same, composition, cured product, display device, solid-state imaging element, sealing material, and insulating material

Abstract

Provided are: a novel compound which has excellent lithography performance and is capable of forming a cured product having a high refractive index; and a method for producing the compound. A compound represented by formula (I) [In formula (I), L represents a single bond or a divalent group, and a plurality of L may be the same or different. A represents an oxygen atom or a sulfur atom, and a plurality of A may be the same or different. And n represents an integer of 0 to 6. R represents a monovalent substituent, and when a plurality of R are present, the plurality of R may be the same as or different from each other. And R2 represents a hydrogen atom or a monovalent substituent, and a plurality of R2 may be the same as or different from each other. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a compound and a method for producing the same, a composition, a cured product, a display device, a solid-state imaging element, a sealing material, and an insulating material. Background Art

[0002] In the field of optical devices, high refractive materials are urgently needed. A lens can be obtained using a high refractive material, and a lens can be used to control the light path in an optical device. In a solid-state imaging element, a lens is used to improve the efficiency of focusing light on each photoelectric conversion element, and in a display device, a lens is used to improve the efficiency of extracting light from a pixel. 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] One object of the present invention is to provide a novel compound having excellent photolithography performance and capable of providing a cured product showing a high refractive index, and a method for producing the same. Another object of the present invention is to provide a composition containing the compound, a cured product of the compound or the composition, a display device containing the cured product, a solid-state imaging element containing the cured product, and a sealing material and an insulating material containing the composition.

[0007] The present invention includes the following contents.

[0008] [1] A compound represented by formula (I).

[0009]

[0010] [In formula (I),

[0011] L represents a single bond or a divalent group, and plural L's may be the same or different.

[0012] A represents an oxygen atom or a sulfur atom, and plural A's may be the same or different.

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

[0014] R represents a monovalent substituent, and when a plurality of Rs exist, the plurality of Rs may be the same or different.

[0015] R 2 represents a hydrogen atom or a monovalent substituent, and there are multiple R 2 Can be the same or different.]

[0016] [2] A composition comprising the compound described in [1].

[0017] [3] The composition according to [2], further comprising a polymerization initiator.

[0018] [4] The composition according to [3], wherein the polymerization initiator is a thermal cationic polymerization initiator or a thermal anionic polymerization initiator.

[0019] [5] A cured product, which is a cured product of the compound described in [1] or the composition described in any one of [2] to [4].

[0020] [6] A display device comprising the cured product described in [5].

[0021] [7] A solid-state imaging device comprising the cured product described in [5].

[0022] [8] A sealing material comprising the compound described in [1] or the composition described in any one of [2] to [4].

[0023] [9] An insulating material comprising the compound described in [1] or the composition described in any one of [2] to [4].

[0024]

[10] A method for producing a compound represented by formula (I-A),

[0025]

[0026] [In formula (I-A),

[0027] L represents a single bond or a divalent group, and plural L's may be the same or different.

[0028] n represents any integer from 0 to 6.

[0029] R represents a monovalent substituent, and when a plurality of Rs exist, the plurality of Rs may be the same or different.

[0030] R 2 represents a hydrogen atom or a monovalent substituent, and there are multiple R 2 Can be the same or different.]

[0031] The production method includes the step of reacting a compound represented by formula (II) with a compound represented by formula (III) to obtain a compound represented by formula (I-A).

[0032]

[0033] [In formula (II), n and R have the same meanings as above.]

[0034]

[0035] [In formula (III), R 2 represents the same meaning as above, and X represents a leaving group.]

[0036]

[11] A method for producing a compound represented by formula (I-B).

[0037]

[0038] [In formula (I-B),

[0039] L represents a single bond or a divalent group, and plural L's may be the same or different.

[0040] A 2 Represents oxygen or sulfur atoms, and there are multiple A 2 Can be the same or different. 2 At least one of them is a sulfur atom.

[0041] n represents any integer from 0 to 6.

[0042] R represents a monovalent substituent, and when a plurality of Rs exist, the plurality of Rs may be the same or different.

[0043] R 2 represents a hydrogen atom or a monovalent substituent, and there are multiple R 2 Can be the same or different.]

[0044] The production method includes the step of reacting the compound represented by formula (I-A) with a sulfiding agent to obtain the compound represented by formula (I-B).

[0045]

[0046] [In formula (I-A), L, n, R and R 2 Means the same as above.]

[0047] According to the present invention, it is possible to provide a novel compound and a method for manufacturing the same having excellent photolithography performance and being able to form a cured product showing a high refractive index. In addition, it is possible to provide a composition containing the compound, a cured product of the compound or the composition, a display device comprising the cured product, a solid-state imaging element comprising the cured product, and a sealing material and an insulating material comprising the composition. The composition comprising the compound is also excellent in terms of curability (film thickness retention). DETAILED DESCRIPTION

[0048] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0049] In this specification, the numerical range represented by "~" represents a range including the numerical values ​​recorded before and after "~" as the minimum and maximum values, respectively. In the numerical range recorded in stages in this specification, the upper limit or lower limit recorded in one numerical range can be replaced by the upper limit or lower limit of another numerical range recorded in stages. In addition, in the numerical range recorded in this specification, the upper limit or lower limit of its numerical range can be replaced by the value shown in the embodiment.

[0050] In this specification, (meth)acrylate refers to acrylate or its corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl, (meth)acrylate, etc.

[0051] In this specification, the materials exemplified below may be used alone or in combination within the range that meets the conditions unless otherwise specified. The content of each component, when there are multiple substances belonging to each component, represents the total amount of the multiple substances unless otherwise specified.

[0052] The compound of one embodiment is a compound represented by formula (I) (hereinafter, sometimes referred to as "compound (I)"). Compound (I) has excellent photolithography performance and can form a cured product having a high refractive index.

[0053]

[0054] In formula (I),

[0055] L represents a single bond or a divalent group, and plural L (if two L exist) may be the same or different.

[0056] A represents an oxygen atom or a sulfur atom, and plural (two) A's may be the same or different.

[0057] n represents any integer from 0 to 6.

[0058] R represents a monovalent substituent, and when a plurality of Rs exist, the plurality of Rs may be the same or different.

[0059] R 2 represents a hydrogen atom or a monovalent substituent, and when there are plural (or two) R 2 Can be the same or different.

[0060] In compound (I), two groups represented by the following formula (X) may be bonded to any position of the 1-8 position of the naphthalene ring. The group represented by formula (X) on the naphthalene ring may be bonded to, for example, any position of the 1-4 position and any position of the 5-8 position (1-4 position). The same applies to the two -SH groups in the compound represented by formula (II).

[0061]

[0062] In formula (X), L, A and R 2 represents the same meaning as above, and * represents a bonding position.

[0063] When compound (I) has one or more monovalent substituents represented by R, the monovalent substituent represented by R may be bonded to any position of positions 1 to 8 of the naphthalene ring except the bonding position of the group represented by formula (X).

[0064] L represents a single bond or a divalent group, and multiple Ls may be the same or different. Examples of divalent groups represented by L include divalent aliphatic chain hydrocarbon groups that may have substituents; divalent alicyclic hydrocarbon groups that may have substituents; divalent aromatic hydrocarbon groups that may have substituents; divalent hydrocarbon groups composed of combinations thereof (e.g., aralkylene groups), and the like. The methylene group (-CH2-) contained in the divalent group may be -O-, -S-, -NR- 1A -(R 1A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, or -SO2-.

[0065] As the divalent aliphatic chain hydrocarbon group, for example, a saturated or unsaturated aliphatic chain hydrocarbon group can be mentioned. More specifically, methylene, ethylene, propylene, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl, undecanediyl, dodecanediyl, tridecanediyl, tetradecanediyl, pentadecanediyl, hexadecanediyl, heptadecanediyl, octadecanediyl, nonanediyl, icosanediyl and other chain hydrocarbon groups 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 particularly preferably 1 or 2.

[0066] 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; a cyano group, and the like.

[0067] Examples of the divalent alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups. More specifically, monocyclic alicyclic hydrocarbon groups such as cyclopropyldiyl, cyclobutyldiyl, cyclopentyldiyl, cyclohexyldiyl, 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.

[0068] Examples of substituents 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; cyano, and the like.

[0069] The divalent aromatic hydrocarbon group may be monocyclic or polycyclic. Examples of the divalent aromatic hydrocarbon group include phenylene, naphthylene, anthracenediyl, fluorenediyl, etc. The number of carbon atoms in the divalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0070] Examples of substituents 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; cyano; and the like.

[0071] In compound (I), in one embodiment, at least one of the two Ls is preferably an alkanediyl group, and more preferably both are alkanediyl groups. In this case, the number of carbon atoms of the alkanediyl group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 or 2. In another embodiment, in the two Ls, at least one is preferably a single bond, and more preferably both are single bonds.

[0072] A represents an oxygen atom or a sulfur atom, and a plurality of A's may be the same or different. When two A's are present, preferably at least one is a sulfur atom, and more preferably both are sulfur atoms. There is a tendency that as the number of sulfur atoms as A increases, a cured product showing a higher refractive index can be provided. In another embodiment, when two A's are present, at least one is an oxygen atom, and more preferably both are oxygen atoms.

[0073] n represents any integer of 0 to 6. n is preferably any integer of 0 to 3, more preferably any integer of 0 to 2, further preferably 0 or 1, and particularly preferably 0.

[0074] R represents a monovalent substituent. When there are multiple Rs, the multiple Rs may be the same or different, and may be the same. Examples of the monovalent substituent represented by R include monovalent aliphatic chain hydrocarbon groups which may have a substituent, monovalent alicyclic hydrocarbon groups which may have a substituent, monovalent aromatic hydrocarbon groups which may have a substituent, and monovalent hydrocarbon groups composed of combinations thereof (e.g., aralkyl groups); hydroxyl groups; amino groups which may be substituted with one or two alkyl groups having 1 to 6 carbon atoms, such as amino, monomethylamino, monoethylamino, dimethylamino, diethylamino, and methylethylamino; pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, Heterocyclic groups such as aliphatic heterocyclic groups having 4 to 20 carbon atoms, such as oxazolinyl, thiazolyl, piperidinyl, morpholinyl, piperazinyl, indolyl, isoindolyl, quinolyl, thienyl, pyrrolyl, furanyl, etc.; halogen atoms; nitro; cyano; carboxyl; sulfo; thiol; formyl; -SF3; -SF5. The methylene group (-CH2-) contained in the monovalent substituent may be replaced by -O-, -S-, -NR 1B -(R 1B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, or -SO2-. It should be noted that examples of the group in which the methylene group (-CH2-) contained in the monovalent substituent is replaced by -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.

[0075] As the monovalent aliphatic chain hydrocarbon group, for example, a saturated or unsaturated aliphatic chain hydrocarbon group can be mentioned. More 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 particularly preferably 1 or 2.

[0076] 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; a cyano group, and the like.

[0077] Examples of the monovalent alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups. More specifically, examples include 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.

[0078] Examples of substituents 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; cyano; and the like.

[0079] The monovalent aromatic hydrocarbon group may be a monocyclic or polycyclic group. Examples of the monovalent aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, fluorenyl, etc. The number of carbon atoms in the monovalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0080] Examples of substituents 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; cyano; and the like.

[0081] R 2 represents a hydrogen atom or a monovalent substituent, and there are multiple R 2 Can be the same or different, can be the same. 2 The monovalent substituent represented by can be exemplified by the same groups as the monovalent substituent represented by R. In compound (I), two R 2 It 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.

[0082] Examples of compound (I) include compounds represented by 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), formula (Ie-2), formula (If-1), and formula (If-2). In these formulas, L, A, n, R, and R 2Means the same as above.

[0083]

[0084] Specific examples of compound (I) are shown below, but compound (I) is not limited thereto.

[0085]

[0086]

[0087]

[0088] From the viewpoint of synthesis, the molecular weight of compound (I) is preferably 2000 or less, more preferably 1000 or less, and further preferably 750 or less. From the viewpoint of volatility, the molecular weight of compound (I) is preferably 50 or more, more preferably 100 or more, and further preferably 150 or more.

[0089] <Method for producing compound>

[0090] Compound (I) includes a compound represented by formula (I-A) (hereinafter, sometimes referred to as “compound (I-A)”) and a compound represented by formula (I-B) (hereinafter, sometimes referred to as “compound (I-B)”).

[0091]

[0092] In formula (I-A), L, n, R and R 2 It has the same meaning as the above (Formula (I)).

[0093]

[0094] In formula (I-B), L, n, R and R 2 A has the same meaning as in the above formula (I). 2 A represents an oxygen atom or a sulfur atom, if there are two or more of them 2 Can be the same or different. 2 At least one of them is a sulfur atom. In compound (I-B), there are two A 2 Preferably, both are sulfur atoms.

[0095] A method for producing compound (I-A) according to one embodiment includes the step of obtaining compound (I-A) by reacting a compound represented by formula (II) (hereinafter, sometimes referred to as “compound (II)”) with a compound represented by formula (III) (hereinafter, sometimes referred to as “compound (III)”).

[0096]

[0097] In formula (II), n and R have the same meanings as described above.

[0098]

[0099] In formula (III), R 2 represents the same meaning as above, and X represents a leaving group.

[0100] The reaction of compound (II) and compound (III) can be carried out in the presence of a base. 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 (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), pyridine, 2,6-lutidine, 2,6-di-tert-butylpyridine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, and tetramethylammonium chloride. The amount of the base to be used is, for example, 0.01 to 10 mol, preferably 0.5 to 5 mol, based on 1 mol of compound (II).

[0101] In compound (III), as the leaving group represented by X, there can be mentioned halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propanesulfonyl, butanesulfonyl, trifluoromethylsulfonyl, perfluoroethylsulfonyl, perfluoropropanesulfonyl, perfluorobutanesulfonyl; arylsulfonyl groups such as benzenesulfonyl, p-toluenesulfonyl, p-fluorobenzenesulfonyl, pentafluorobenzenesulfonyl, etc. As specific examples of compound (III), epihalohydrin compounds (L is methylene, m is 0, R 2 is a hydrogen atom, and X is a halogen atom). The amount of compound (III) to be used is, for example, 0.01 to 20 mol, preferably 0.5 to 15 mol, relative to 1 mol of compound (II). In this step, the reaction may be carried out using two or more compounds (III).

[0102] 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 diethers, esters, aliphatic nitriles, sulfoxides, and amides can be cited. As the organic solvent, the following solvents can be exemplified.

[0103] 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.

[0104] Aromatic hydrocarbons: benzene, toluene, xylene, mesitylene, naphthalene, anisole, nitrobenzene, aniline, tetralin, durene, etc.

[0105] Halogenated aromatic hydrocarbons: chlorobenzene, dichlorobenzene, chloronaphthalene, etc.

[0106] Aliphatic hydrocarbons: pentane, hexane, heptane, etc.

[0107] Halogenated aliphatic hydrocarbons: dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, tetrachloroethylene, etc.

[0108] Ethers: diethyl ether, diisopropyl ether, methyl tert-butyl ether, cyclopentyl methyl ether, diphenyl ether, dimethoxyethane, di Alkane, etc.

[0109] Alcohols: methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, hexafluoroisopropanol, etc.

[0110] Glycol diethers: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, etc.

[0111] Esters: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc.

[0112] Aliphatic nitriles: acetonitrile, etc.

[0113] Sulfoxides: dimethyl sulfoxide, sulfolane, etc.

[0114] Amides: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0115] The temperature for the reaction of compound (II) and compound (III) is, for example, -80 to 200°C, preferably 0 to 150°C.

[0116] In this way, compound (I-A) can be obtained. When the obtained compound (I-A) is used in the synthesis of compound (I-B), compound (I-A) may be isolated and used, or may be used in the method for producing compound (I-B) without isolation.

[0117] The method for producing compound (I-B) of one embodiment comprises the step of obtaining compound (I-B) by reacting compound (I-A) with a sulfiding agent. The method for producing compound (I-B) may further comprise the step of obtaining compound (I-A) by reacting the above-mentioned compound (II) with compound (III) before the step of obtaining compound (I-B).

[0118] The reaction of compound (I-A) with a sulfiding agent is a reaction in which the oxygen atom of the oxetanyl ring of compound (I-A) is substituted with a sulfur atom using a sulfiding agent to form a thietane ring. Examples of the sulfiding agent include thiourea, methylthiourea, dimethylthiourea, trimethylthiourea, tetramethylthiourea, tetraethylthiourea, ethylenethiourea, phenylthiourea, diphenylthiourea, tolylthiourea, xylylthiourea, sodium thiocyanate, potassium thiocyanate, and the like. The amount of the sulfiding agent used can be arbitrarily adjusted according to the oxygen atom to be substituted. 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 compound (I-A). In addition, by adjusting the amount of the sulfiding agent used, the reaction temperature, the reaction time, and the like, both of the oxygen atoms in compound (I-A) can be substituted with sulfur atoms, or one of the oxygen atoms in compound (I-A) can be substituted with a sulfur atom.

[0119] The reaction of compound (I-A) and the sulfiding agent is preferably carried out in a solvent. Examples of the solvent include the solvents exemplified in the reaction of compound (II) and compound (III). The reaction of compound (I-A) and the sulfiding agent is carried out at, for example, -80 to 200°C, preferably 0 to 100°C.

[0120] In order to inhibit the polymerization of the generated compound (I-B), a polymerization inhibitor may be added to the reaction system. Examples of the polymerization inhibitor include acids and acid anhydrides. More specifically, examples include:

[0121] Inorganic acidic compounds such as nitric acid, hydrochloric acid, perchloric acid, hypochlorous acid, chlorine dioxide, hydrofluoric acid, sulfuric acid, oleum, sulfuryl 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, anhydrous nitric acid, anhydrous sulfuric acid, boric oxide, arsenic pentoxide, phosphorus pentoxide, anhydrous chromic acid, silicon dioxide, aluminum oxide, aluminum chloride, zinc chloride, lithium hydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, cesium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, etc.

[0122] Organic carboxylic acids such as formic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, propionic acid, butyric acid, succinic acid, valeric acid, caproic acid, octanoic acid, cycloalkane acid, methyl mercaptopropionate, malonic acid, glutaric acid, adipic acid, cyclohexanecarboxylic acid, thiodipropionic acid, dithiodipropionic acid, maleic acid, benzoic acid, phenylacetic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic acid, salicylic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, benzoylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, benzyl 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, and trifluoroacetic anhydride;

[0123] Phosphoric acids such as monomethyl phosphate, dimethyl phosphate and trimethyl phosphate, monoethyl phosphate, diethyl phosphate and triethyl phosphate, monoisobutyl phosphate, diisobutyl phosphate and triisobutyl phosphate, monobutyl phosphate, dibutyl phosphate and tributyl phosphate, monolauryl phosphate, dilauryl phosphate and trilauryl phosphate, and phosphorous acids obtained by converting their phosphate esters into phosphites;

[0124] Organophosphorus compounds such as dialkyl dithiophosphoric acids represented by dimethyl dithiophosphoric acid;

[0125] Phenol, catechol, tert-butylcatechol, 2,6-di-tert-butylcresol, 2,6-di-tert-butylethylphenol, resorcinol, hydroquinone, phloroglucinol, pyrogallol, cresol, ethylphenol, butylphenol, nonylphenol, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, hydroxyphenylacetic acid amide, hydroxyphenylacetic acid methyl ester, hydroxyphenylethyl acetate, 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;

[0126] 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.

[0127] The amount of the polymerization inhibitor used is, for example, 0.0001 to 1.0 mol, preferably 0.01 to 0.2 mol, relative to 1 mol of compound (I-B). The polymerization inhibitor is preferably acetic acid, acetic anhydride, maleic acid, maleic anhydride, phosphoric acid, an alkali metal hydrogen phosphate, or an alkali metal dihydrogen phosphate.

[0128] The product solution after the reaction can improve the stability of the obtained compound (I-B) over time by washing with an acidic aqueous solution. Specific examples of the acid used in the acidic aqueous solution include 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. There is a tendency that the aqueous solution of these acids usually shows an effect below pH 6, and the more effective range is below pH 3. The acid used in the acidic aqueous solution is preferably hydrochloric acid, sulfuric acid, phosphoric acid or maleic acid.

[0129] Furthermore, a hydrogen sulfide adsorbent may be used to improve the stability of compound (I-B). Examples of hydrogen sulfide adsorbents include iron (III) hydroxide, zinc oxide, KNK-301 (zinc oxide adsorbent, manufactured by Kureha Oil & Fats Industries Co., Ltd.), NIONON 202A (iron oxide adsorbent, manufactured by Ibuki Masaru Co., Ltd.), and LIMONIC (iron hydroxide adsorbent, manufactured by Nippon Limonite Co., Ltd.). The hydrogen sulfide adsorbent may be added during the reaction or used in the purification after the reaction.

[0130] <Composition>

[0131] The composition of one embodiment contains compound (I). In addition to compound (I), the composition may further contain other components except compound (I). Due to the tendency that compound (I) is easy to solidify, the composition can be solidified by irradiation or heating of active energy rays. By solidifying the composition, a molded object containing a solidified material of the composition can be formed. Here, a molded object refers to an object containing a solidified material of the composition and molded into a desired shape.

[0132] The content of compound (I) in the composition is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, particularly preferably 20% by mass or more, and most preferably 30% by mass or more, and is preferably 100% by mass or less, more preferably 99% by mass or less, further preferably 95% by mass or less, particularly preferably 90% by mass or less, and most preferably 85% by mass or less, relative to the total amount of solid components of the composition.

[0133] The total amount of solid content of the composition refers to the total amount of components contained in the composition excluding the solvent. The content of each component in the solid content of the composition can be measured by known analytical means such as liquid chromatography and gas chromatography. The content of each component in the solid content of the composition can be calculated based on the formulation when the composition is prepared.

[0134] Examples of other components contained in the composition include resins, curable compounds other than compound (I), polymerization initiators, solvents, additives, etc. Examples of additives include inorganic particles, fillers, polymerization initiator aids, sensitizers, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, ultraviolet absorbers, antioxidants, dispersants, etc.

[0135] (1) Resin

[0136] The composition may contain one or more resins. By making the composition contain a resin, it is possible to impart developability to the cured product of the composition, adjust the mechanical properties and / or optical properties of the cured product and the molded product containing the cured product. As the resin, for example, 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.

[0137] As thermoplastic resins, for example, olefin resins such as polyethylene resins, polypropylene resins, and polycycloolefin resins; (meth) acrylic resins such as poly(meth) acrylate resins; styrene resins such as polystyrene resins, styrene-acrylonitrile resins, and acrylonitrile-butadiene-styrene resins; vinyl resins such as polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, polyvinyl butyral resins, ethylene-vinyl acetate copolymers, and ethylene-vinyl alcohol resins; polyester resins such as polyethylene terephthalate resins, polybutylene terephthalate resins, and liquid crystal polyester resins; polyoxymethylene resins; polyamide resins; polycarbonate resins; polyurethane resins; polyphenylene sulfide resins, etc. One or more of these resins may be used in the form of a polymer blend or a polymer alloy.

[0138] Examples of the curable resin include resins having a photopolymerizable group or a thermally polymerizable group, and more specifically, include (meth)acrylic resins, epoxy resins, melamine resins, unsaturated polyester resins, phenolic resins, urea-formaldehyde resins, alkyd resins, polyimide resins, and the like.

[0139] As another example of the resin, an alkali-soluble resin can be cited. By making the composition contain an alkali-soluble resin, it is possible to impart developability to the cured product of the composition. The alkali-soluble resin refers to a resin that is soluble in an alkaline aqueous solution. Specifically, for example, a resin having a carboxyl group and / or a phenolic hydroxyl group can be cited.

[0140] From the viewpoint of improving the developability and solvent resistance of the cured product of the composition, the acid value of the alkali-soluble resin is preferably 10 to 170 mgKOH / g, more preferably 20 to 150 mgKOH / g, and further preferably 30 to 140 mgKOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the alkali-soluble resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

[0141] Another example of the resin is a high refractive index resin, which is a resin having a refractive index of 1.60 or more at a wavelength of 550 nm.

[0142] The weight average molecular weight (Mw) of the resin measured by gel permeation chromatography (GPC) in terms of standard polystyrene is, for example, 5 to 2 million, preferably 1,000 to 1 million, and more preferably 1,500 to 750,000. The Mw of the resin can be adjusted by appropriately combining the selection of the raw materials used, the charging method, the reaction temperature, the reaction time and other reaction conditions.

[0143] When the composition contains a resin, the content of the resin in the composition is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, based on the total solid content of the composition.

[0144] (2) Curable compounds other than compound (I)

[0145] The composition may contain one or more curable compounds other than compound (I). By containing a curable compound other than compound (I), the viscosity or curability of the composition can be adjusted, and the mechanical properties and / or optical properties of the obtained cured product and the molded product containing the cured product can be adjusted.

[0146] Examples of curable compounds other than compound (I) include episulfide compounds, epoxy compounds, oxetane compounds other than compound (I), thietane compounds other than compound (I), hydroxy compounds, carboxyl compounds, vinyl ether compounds, allyl compounds, thiol compounds, polyphenol compounds, iso(thio)cyanate compounds, (meth)acrylate compounds, and acid anhydrides.

[0147] When the composition contains a curable compound other than compound (I), the content of the curable compound in the composition is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, relative to the total amount of the solid content of the composition.

[0148] (3) Polymerization initiator

[0149] The composition 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 compound (I), for example, free radical polymerization initiator, cationic polymerization initiator, anionic polymerization initiator, free radical and cationic polymerization initiator, etc. can be cited. These polymerization initiators generate free radicals, acids or bases by at least one of the irradiation of active energy rays and heat, and generate free radical polymerization, cationic polymerization or anionic polymerization of compound (I). It should be noted that compound (I) can be polymerized and cured by at least one of the irradiation of active energy rays and heat even in the absence of a polymerization initiator.

[0150] Examples of free radical polymerization initiators that initiate free radical polymerization by heat include organic peroxides such as hydrogen peroxide and perbenzoic acid, and azo compounds such as azobisbutyronitrile. Examples of photoradical polymerization initiators that initiate free radical polymerization by irradiation with active energy rays include oxime compounds, alkylphenone compounds, arylketone compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds.

[0151] The cationic polymerization initiator is a compound that can release a substance that initiates cationic polymerization by at least one of irradiation with active energy rays and heat. Examples of the cationic polymerization initiator include iodine Onium salts, sulfonium salts, ammonium salts, cyclopentadienyl iron (II) complexes, etc. They can initiate cationic polymerization by at least one of irradiation with active energy rays and heat according to the difference in structure. It should be noted that the compound that can release a substance that initiates cationic polymerization by irradiation with active energy rays is called a photocationic polymerization initiator, and the compound that can release a substance that initiates cationic polymerization by heat is called a thermal cationic polymerization initiator.

[0152] Anionic polymerization initiators are compounds that can release substances that initiate anionic polymerization by at least one of irradiation with active energy rays and heat. Examples of anionic polymerization initiators include ammonium salts, DBU (diazabicycloundecene) salts, DBN (diazabicyclononene) salts, biguanide salts, aromatic Salts, aromatic dimethyl urea, aliphatic dimethyl urea, etc. They can initiate anionic polymerization by at least one of irradiation with active energy rays and heat according to the difference in structure. Compounds that can release substances that initiate anionic polymerization by irradiation with active energy rays are called photoanionic polymerization initiators, and compounds that can release substances that initiate anionic polymerization by heat are called thermal anionic polymerization initiators.

[0153] When the composition contains a polymerization initiator, from the viewpoint of improving the heat resistance of the composition and its cured product, the composition preferably contains a thermal cationic polymerization initiator or a thermal anionic polymerization initiator, and more preferably contains a thermal anionic polymerization initiator. On the other hand, from the viewpoint of improving photolithographic performance, the composition preferably contains a photocationic polymerization initiator.

[0154] When the composition contains a polymerization initiator, the content of the polymerization initiator in the composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, based on 100 parts by mass of the total of compound (I) and other curable compounds, from the viewpoint of improving curability, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, from the viewpoint of improving the mechanical properties and other physical properties of the cured product.

[0155] (4) Solvent

[0156] The composition may contain one or more solvents. The solvent is preferably a solvent capable of dissolving or dispersing compound (I), and more preferably a solvent capable of further dissolving or dispersing other components other than compound (I). As the solvent, for example, the solvents exemplified in the reaction between compound (II) and compound (III) can be exemplified. As solvents other than these solvents (organic solvents), for example, ether esters such as methyl methoxyacetate, ethyl methoxyacetate, methyl 3-methoxypropionate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol monomethyl ether acetate can be cited.

[0157] When the composition contains a solvent, the content of the solvent in the composition is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, relative to 100 parts by mass of the solid content of the composition. When the composition contains a solvent, the solid content concentration of the composition is preferably 5 to 60% by mass, more preferably 10 to 50% by mass.

[0158] <Cured products and molded products>

[0159] The solidified material of one embodiment is a solidified material of compound (I) or a solidified material of a composition. The molded material of one embodiment includes a solidified material. Compound (I) and composition are excellent in film forming property and curing property, so they can be used as curable materials for making solidified materials or molded materials including the solidified materials. The solidified material can be obtained by curing compound (I) or a composition by utilizing at least one of the irradiation of active energy rays and heat. The shape of the molded material including the solidified material is not particularly limited, and can include a sheet (film) shape, a plate shape, a lens shape, a powdery shape, a granular shape, a non-spherical particle shape, a crushed particle shape, a porous shape, a blocky continuum, a fiber shape, a tubular shape, a hollow filament shape, etc., and can be any shape according to the purpose of the molded material.

[0160] The method for obtaining a molded product from the composition 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.

[0161] In the cast polymerization molding method, for example, compound (I) or the composition 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 also be further irradiated with active energy rays for additional curing.

[0162] In the case of forming a film as a molded object on a substrate, compound (I) or a composition is applied to a substrate, dried as needed to form a coating film (coating layer), and the coating film (coating layer) is cured, thereby obtaining a molded object as a cured film (cured layer). The molded object may also be a patterned cured film (cured layer). The patterned cured film may be obtained by patterning using methods such as photolithography, inkjet, and printing. Patterning methods may be, for example, photolithography. Photolithography is a method of applying a compound (I) or a composition to a substrate, drying as needed to form a coating film (coating layer), exposing the coating film (coating layer) across a photomask, and developing the exposed coating film (coating layer).

[0163] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass with silicon dioxide coated on the surface, and alkali-free glass; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; and substrates having aluminum, silver, or a silver / copper / palladium alloy thin film formed thereon. Examples of a method for coating the compound (I) or the composition on the substrate include spin coating, slit coating, and slit and spin coating.

[0164] The light source used in the exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, from the light with wavelengths in these ranges, light near 436 nm, near 408 nm, or near 365 nm can be selectively extracted using a bandpass filter according to the absorption wavelength of the photopolymerization initiator. Specific examples of the light source include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, etc. After the pattern exposure, the exposed coating film (coating layer) can be heated before development (baking before development).

[0165] As the developer used in the development, for example, aqueous solutions and solvents containing alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide (TMAH), etc. can be cited. As the solvent, for example, the solvent (organic solvent) exemplified in the reaction between compound (II) and compound (III) can be exemplified. The developer can contain a surfactant. As the development method, a spin-capping immersion method, an immersion method, a spray method, etc. can be cited. The patterned cured film (cured layer) obtained by development can be further heated (post-baked).

[0166] The cured product or the molded product containing the cured product is formed by compound (I) or a composition containing compound (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, etc. The refractive index of the cured product or the molded product containing the cured product at a wavelength of 550nm can be 1.60 or more, 1.65 or more, 1.70 or more, or 1.72 or more. The refractive index of the cured product or the molded product containing the cured product at a wavelength of 550nm is, for example, less than 1.80, or less than 1.78.

[0167] The refractive index of a cured product or a molded product containing the cured product at a wavelength of 550 nm can be measured, for example, by the following method. First, a coating film is formed on a substrate, and the coating film is cured to obtain a substrate on which a cured film is formed. Next, a UV-visible spectrophotometer (e.g., "V-650" manufactured by JASCO Corporation) with an integrating sphere unit (e.g., "ISV-922" manufactured by JASCO Corporation) is used to measure the transmission spectrum and reflection spectrum of the substrate with a wavelength of 300 nm to 800 nm. Next, in the transmission spectrum and the true reflection spectrum obtained by smoothing the increase and decrease of the reflection spectrum due to interference subtracted from the reflection spectrum, the refractive index of the cured product or the molded product containing the cured product at a wavelength of 550 nm is calculated based on the Fresnel formula (e.g., Hecht Optics I Original Works 5th Edition, Maruzen Publishing, 2018, p. 209-226). Thereby, the refractive index of the cured product or the molded product including the cured product at a wavelength of 550 nm can be determined.

[0168] <Purpose>

[0169] As the uses of the cured or molded products, for example, there can be mentioned glass substitutes and surface coating materials thereof; coating materials for window glass, lighting glass and light source protection glass of houses, facilities, transportation equipment, etc.; window films of houses, facilities, transportation equipment, etc.; interior and exterior decoration materials and interior and exterior decoration coatings and coating films formed by the coatings of houses, facilities, transportation equipment, etc.; alkyd resin paint coatings and coating films formed by the coatings; acrylic paint coatings and coating films formed by the coatings; parts for light sources emitting ultraviolet rays such as fluorescent lamps and mercury lamps; parts for precision machinery, electronic and electrical equipment, and materials for blocking electromagnetic waves generated by various displays; containers or packaging materials for foods, chemicals, drugs, etc.; bottles, boxes, blisters, cups, special packaging, optical disc coatings, sheets or films for agricultural industry; anti-fading agents for printed materials, dyed materials, dyes, etc.; polymer supports (for example, machinery and protective films for plastic parts of automobile parts); outer coatings for printed materials; inkjet media coatings; laminated matte films; optical lighting films; intermediate layers of safety glass / windshields; electrochromic / photochromic applications; superlaminated films; solar control films; cosmetics such as sunscreens, shampoos, conditioners, and hair products; fiber products and fibers for clothing such as sportswear, stockings, and hats; home interior decorations such as curtains, carpets, and wallpapers; medical devices such as plastic lenses, contact lenses, and artificial eyes; optical products such as filters, backlight display films, prisms, lenses (for example, eyeglass lenses, camera lenses, and microlenses and reading 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.

[0170] The molded article is suitable for use 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 light-gathering efficiency of 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. Examples of display devices include liquid crystal display devices and organic EL display devices.

[0171] As high refractive index materials, inorganic compounds such as zirconium oxide and titanium oxide have been known. However, when making a molded object containing a high refractive index material composed of an inorganic compound, it is sometimes difficult to perform etching, etc., and it is not easy to mold. In addition, there is a situation where the high refractive index material scatters during molding and causes pollution problems. Such problems can be solved by using the high refractive index material of this embodiment as an organic compound.

[0172] The compound (I) and the composition of the present embodiment can be used for sealing materials. The sealing material of one embodiment contains compound (I) or a composition. The photolithography performance of the sealing material of the present embodiment is excellent. The sealing material of the present embodiment can form a solidified product or its molded product with a small linear thermal expansion coefficient (CTE). In addition, the sealing material of the present embodiment can form a solidified product or its molded product with low water absorption and high flexibility. The solidified product or the molded product can be used as various sealing components such as LED sealing material components and semiconductor sealing components. The sealing component can be a sealing film.

[0173] The sealing material of the present embodiment may further contain other components in addition to the compound (I) or the composition. Other components include inorganic fillers, etc. The content of the inorganic filler may be, for example, 0.5 to 10000 parts by mass relative to 100 parts by mass of the compound (I) or the composition.

[0174] The compound (I) and the composition of the present embodiment can be used for insulating materials. An insulating material of one embodiment contains compound (I) or a composition. The lithographic performance of the insulating material of the present embodiment is excellent. The insulating material of the present embodiment can form a cured product or a molded product thereof having excellent dielectric constant and dielectric loss tangent. In addition, the insulating material of the present embodiment can form a cured product or a molded product thereof having a small linear thermal expansion coefficient (CTE). The cured product or the molded product can be used as various insulating components. The insulating component can be an interlayer insulating film.

[0175] The insulating material of the present embodiment may further contain other components in addition to the compound (I) or the composition. Examples of other components include plasticizers, antioxidants, heat stabilizers, antistatic agents, and the like.

[0176] Example

[0177] Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these Examples. It should be noted that, unless otherwise specified, "parts" means "parts by mass".

[0178] [Example 1-1: Synthesis of the compound represented by formula (Ia-1-1)]

[0179] A four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, and 5 parts of the compound represented by formula (IIa-1) (1,6-naphthalenedithiol), 20 parts of N,N-dimethylformamide, 11.9 parts of the compound represented by formula (IIIa-1) (3-oxetanesulfonate) and 42.4 parts of cesium carbonate were added to the flask, and stirred at 60° C. for 7 hours. The obtained mixture was purified to obtain 2.5 parts of the compound represented by formula (Ia-1-1).

[0180]

[0181] LC-MS determination and 1 H-NMR analysis confirmed the formation of the compound represented by formula (Ia-1-1).

[0182] 1 H-NMR (deuterated chloroform) δ: 8.22-8.24 (1H), 7.56-7.64 (2H), 7.36-7.39 (2H), 7.28-7.30 (1H), 4.99-5.10 (4H), 4.65-4.72 (4H), 4.44-4.62 (2H)

[0183] LC-MS: [M+H] + =305.5

[0184] [Example 1-2: Synthesis of the compound represented by formula (Ia-1-1)]

[0185] A four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, 0.4 parts of the compound represented by formula (IIa-1) (1,6-naphthalenedithiol), 4 parts of dimethyl sulfoxide, 0.7 parts of the compound represented by formula (IIIa-2) (3-bromooxetane) and 1.7 parts of cesium carbonate were added to the flask, and stirred at 60° C. for 7 hours. The obtained mixture was purified to obtain 0.3 parts of the compound represented by formula (Ia-1-1).

[0186]

[0187] LC-MS determination and 1 The results of H-NMR analysis were the same as those of Example 1, and it was confirmed that the compound represented by formula (Ia-1-1) was produced.

[0188] [Example 1-3: Synthesis of the compound represented by formula (Ia-1-2)]

[0189] A four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, and 5 parts of the compound represented by formula (IIa-1) (1,6-naphthalenedithiol), 25 parts of acetone, and 7.8 parts of the compound represented by formula (IIIa-3) were added to the flask, and stirred at 25°C for 10 minutes. Next, 2.6 parts of sodium hydroxide and 25 parts of pure water were added to another flask to completely dissolve them, and then added to the four-necked flask. After addition, the temperature was raised to 65°C and stirred at 65°C for 2 hours. The obtained mixture was purified to obtain 6 parts of the compound represented by formula (Ia-1-2).

[0190]

[0191] LC-MS determination and 1 H-NMR analysis confirmed the formation of the compound represented by formula (Ia-1-2).

[0192] 1 H-NMR (deuterated chloroform) δ: 8.32-8.34 (1H), 7.77-7.78 (1H), 7.52-7.59 (3H), 7.37-7.41 (1H), 4.35-4.53 (8H), 3.29-3.38 (4H), 1.44-1.47 (6H)

[0193] LC-MS: [M+H] + =361.5

[0194] [Synthesis Example: Synthesis of the Compound Represented by Formula (X-1)]

[0195] A four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, and 23.5 parts of the compound represented by formula (IIa-1) (1,6-naphthalenedithiol), 117.5 parts of acetone, and 25.4 parts of chloroacetic acid were added to the flask, and stirred in an ice bath for 10 minutes. Next, 19.6 parts of sodium hydroxide and 117.5 parts of pure water were added to another flask to completely dissolve them, and then added to the four-necked flask. After addition, the temperature was raised to 25°C and stirred at 25°C for 3 hours. The obtained mixture was purified to obtain 30 parts of the compound represented by formula (X-1).

[0196]

[0197] [Example 2-1: Preparation of composition]

[0198] 100 parts by mass of the compound represented by formula (Ia-1-1) obtained in Example 1-1 or Example 1-2, 5 parts by mass of polymerization initiator A, and 250 parts by mass of cyclopentanone as a solvent were placed in a flask and stirred to obtain a liquid composition. The obtained composition was visually observed to be transparent, and it was confirmed that the ingredients were uniformly dissolved.

[0199] [Example 2-2: Preparation of composition]

[0200] A liquid composition was obtained in the same manner as in Example 2-1 except that 100 parts by mass of the compound represented by formula (Ia-1-1) was replaced with 100 parts by mass of the compound represented by formula (Ia-1-2) obtained in Example 1-3. The obtained composition was visually observed to be transparent, and it was confirmed that the blended components were uniformly dissolved.

[0201] [Comparative Examples 2-1, 2-2: Preparation of Compositions]

[0202] A liquid composition was obtained in the same manner as in Example 2-1 except that the types of ingredients and their addition amounts in the composition were changed as shown in Table 1. The compositions of Comparative Examples 2-1 and 2-2 were visually observed to be transparent, and it was confirmed that the ingredients were uniformly dissolved.

[0203] The details of the abbreviations of the blending components shown in Table 1 are as follows.

[0204] [1] (Ia-1-1): Compound represented by formula (Ia-1-1) (Example 1-1 or Example 1-2)

[0205] [2] (Ia-1-2): Compound represented by formula (Ia-1-2) (Example 1-3)

[0206] [3] (X1): Compound represented by formula (X-1) (Synthesis Example)

[0207] [4] (Y1): A compound represented by the formula (Y1) (synthesized according to the description of Example 6 of International Publication No. 2023 / 058449)

[0208]

[0209] [5] (Y2): A compound represented by the formula (Y2) (bisphenol A diglycidyl ether, manufactured by DIC Corporation, “EPICLONEX A-850CRP”)

[0210]

[0211] [6] Polymerization initiator A: ammonium salt type thermal cationic polymerization initiator (manufactured by KING INDUSTRIES INC., “CXC-1821”)

[0212] [Evaluation test]

[0213] (1) Refractive index of cured product

[0214] (1-1) Formation of Cured Film (Formation of Cured Film Using Compositions of Examples 2-1, 2-2, and Comparative Examples 2-1, 2-2)

[0215] About 3 mL of the composition prepared in Examples 2-1, 2-2 and Comparative Examples 2-1, 2-2 is dropped onto an alkali-free glass (thickness 0.7 mm, manufactured by Corning Incorporated, “Eagle XG”), and spin-coated at 1000 rpm and 20 seconds using a spin coater (manufactured by MIKASA Co., Ltd., “MS-B100”) to form a coating film. The alkali-free glass plate formed with the coating film is pre-baked and heated at 60°C for 2 minutes. Next, the alkali-free glass plate formed with the coating film is exposed to light in an atmospheric atmosphere at a temperature of 1000 mJ / cm 2 The alkali-free glass plate with the coating film formed thereon was then post-baked and heated at 120°C for 5 minutes to obtain an alkali-free glass with a cured film formed thereon. The film thickness of the cured film on the alkali-free glass was measured using a probe-type film thickness meter (manufactured by Bruker, "DekTak XT"), and the result was 1.5 μm. The curing conditions of the coating film are summarized in Table 1.

[0216] (1-2) Determination of refractive index

[0217] The transmission spectrum and reflection spectrum of the alkali-free glass plate formed with the cured film prepared in (1-1) at a wavelength of 300 nm to 800 nm were measured using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, “V-650”) with an integrating sphere unit (manufactured by JASCO Corporation, “ISV-922”). The refractive index of the cured 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 at a wavelength of 550 nm and the refractive index of the alkali-free glass (manufactured by Corning Incorporated, “Eagle XG”) in the transmission spectrum and the true reflection spectrum obtained by smoothing the increase and decrease of the reflection spectrum due to interference. The results are shown in Table 1.

[0218] (2) Curability (film thickness retention)

[0219] By the same method as in (1-1), alkali-free glass having a cured film formed thereon was obtained using the compositions of Examples 2-1 and 2-2 and Comparative Examples 2-1 and 2-2.

[0220] The obtained cured film of the alkali-free glass was evaluated for curability (film thickness retention) according to the following evaluation criteria. The curability was evaluated by immersing the alkali-free glass formed with the cured film in acetone at 23°C for 10 minutes, based on the change in the appearance of the cured film before and after the immersion and the film thickness retention before and after the immersion (film thickness retention = film thickness of the cured film after immersion ÷ film thickness of the cured film before immersion × 100 (%)). If the result is A or B, it can be said that the curability is good.

[0221] A: No appearance change, film thickness retention rate is 100% to 90%.

[0222] B: There is no change in appearance, and the film thickness retention rate is less than 90% and 80% or more.

[0223] C: No change in appearance, and the film thickness retention rate is less than 80%.

[0224] D: Regardless of the film thickness retention rate, the cured film became cloudy after immersion.

[0225] [Table 1]

[0226]

[0227] [Example 3-1: Preparation of composition]

[0228] 80 parts by mass of the compound represented by formula (Ia-1-1) obtained in Example 1-1 or Example 1-2, 20 parts by mass of the compound represented by formula (X-1), 5 parts by mass of polymerization initiator A, and 250 parts by mass of cyclopentanone as a solvent were placed in a flask and stirred to obtain a liquid composition. The obtained composition was visually observed to be transparent, and it was confirmed that the blending components were uniformly dissolved.

[0229] [Example 3-2: Preparation of composition]

[0230] A liquid composition was obtained in the same manner as in Example 3-1 except that 80 parts by mass of the compound represented by formula (Ia-1-1) was replaced with 80 parts by mass of the compound represented by formula (Ia-1-2) obtained in Example 1-3. The obtained composition was visually observed to be transparent, and it was confirmed that the blended components were uniformly dissolved.

[0231] [Comparative Examples 3-1, 3-2: Preparation of Compositions]

[0232] Liquid compositions were obtained in the same manner as in Example 3-1 except that the types of ingredients and their addition amounts in the composition were changed as shown in Table 2. The compositions of Comparative Examples 3-1 and 3-2 were visually observed to be transparent, and it was confirmed that the ingredients were uniformly dissolved.

[0233] [Evaluation test]

[0234] (3) Lithography performance

[0235] About 3 mL of the composition prepared in Examples 3-1, 3-2 and Comparative Examples 3-1, 3-2 is dropped onto an alkali-free glass (thickness 0.7 mm, manufactured by Corning Incorporated, “Eagle XG”), and spin-coated at 1000 rpm and 20 seconds using a spin coater (manufactured by MIKASA Co., Ltd., “MS-B100”) to form a coating film. The alkali-free glass plate with the coating film formed thereon is heated at 80°C for 2 minutes. Next, the alkali-free glass plate with the coating film formed thereon is exposed to light in an atmospheric atmosphere at a temperature of 1000 mJ / cm 2 The irradiation energy is set through the photomask with a gap of 200μm between the photomask and the coating surface for close exposure. Then, the alkali-free glass plate with the coating film formed after exposure is heated at 80°C for 2 minutes, immersed in a 2.38% by mass aqueous solution of TMAH for 1 minute, and then immersed in pure water for 1 minute for development. Then, a hot plate is used to heat at 120°C for 5 minutes to obtain an alkali-free glass with a patterned cured film. The film thickness of the non-patterned portion of the cured film on the alkali-free glass was measured using a probe-type film thickness meter (DekTak XT, manufactured by Bruker), and the result was 1.5μm.

[0236] The obtained cured film was evaluated for lithography performance according to the following evaluation criteria. The lithography performance was evaluated by observing the cross section of a line / space pattern with a width of 5 μm and a ratio of 1:1, using the top loss rate (=(the difference between the thickness of the non-patterned portion and the patterned portion) ÷ (the thickness of the non-patterned portion) × 100 (%)). The results are shown in Table 2. The smaller the top loss rate, that is, the closer it is to 0%, the better the lithography performance.

[0237] A: The top loss rate is 0% to 10%.

[0238] B: The top loss rate is greater than 10% and less than 20%.

[0239] C: The top loss rate is greater than 20% and less than 40%.

[0240] [Table 2]

[0241]

[0242] As shown in Table 1 and Table 2, the composition of the embodiment is superior to the composition of the comparative example in terms of the refractive index and photolithography performance of the cured product. In addition, it is found that the composition of the embodiment is also excellent in terms of curability (film thickness retention). According to these results, it is confirmed that the photolithography performance of the compound of the present invention is excellent and a cured product showing a high refractive index can be formed.

Claims

1. A compound represented by formula (I), In formula (I), L represents a single bond or a divalent group, and a plurality of Ls may be the same or different. A represents an oxygen atom or a sulfur atom, and a plurality of A's may be the same or different. n represents any integer from 0 to 6, R represents a monovalent substituent. When there are multiple R groups, the multiple R groups may be the same or different. R 2 represents a hydrogen atom or a monovalent substituent, and there are multiple R 2 Same or different.

2. A composition comprising the compound according to claim 1.

3. The composition according to claim 2, wherein It further contains a polymerization initiator.

4. The composition according to claim 3, wherein The polymerization initiator is a thermal cationic polymerization initiator or a thermal anionic polymerization initiator. 5 . A cured product, which is a cured product of the compound according to claim 1 or the composition according to any one of claims 2 to 4. A display device comprising the cured product according to claim 5. 7 . A solid-state imaging element comprising the cured product according to claim 5 . 8 . A sealing material comprising the compound according to claim 1 or the composition according to any one of claims 2 to 4.

9. An insulating material comprising the compound according to claim 1 or the composition according to any one of claims 2 to 4.

10. A method for producing a compound represented by formula (I-A), In formula (I-A), L represents a single bond or a divalent group, and a plurality of Ls may be the same or different. n represents any integer from 0 to 6, R represents a monovalent substituent. When there are multiple R groups, the multiple R groups may be the same or different. R 2 represents a hydrogen atom or a monovalent substituent, and there are multiple R 2 Same or different; The production method comprises the steps of: obtaining the compound represented by the formula (I-A) by reacting the compound represented by the formula (II) with the compound represented by the formula (III); In formula (II), n and R have the same meanings as n and R in formula (I-A), In formula (III), R 2 represents the same as R in the formula (I-A) 2 The same meaning, X represents a leaving group.

11. A method for producing a compound represented by formula (I-B), In formula (I-B), L represents a single bond or a divalent group, and a plurality of Ls may be the same or different. A 2 Represents oxygen or sulfur atoms, and there are multiple A 2 Same or different, where A 2 At least one of is a sulfur atom, n represents any integer from 0 to 6, R represents a monovalent substituent. When there are multiple R groups, the multiple R groups may be the same or different. R 2 represents a hydrogen atom or a monovalent substituent, and there are multiple R 2 Same or different; The production method comprises the steps of: obtaining the compound represented by the formula (I-B) by reacting the compound represented by the formula (I-A) with a sulfiding agent, In formula (I-A), L, n, R and R 2 represents L, n, R and R in the above formula (I-B) 2 Same meaning.

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