Composition and its cured products, molded products, display devices, solid-state image sensors, and light guide plates

Abstract

To provide a composition that can yield a cured product exhibiting a high refractive index and also possesses good storage stability. [Solution] A composition is provided that contains a compound (A) having a thiirane group or a thietan group, an acid generator (B), and an amine compound (C) having a boiling point of 200°C or higher.

Description

[Technical Field]

[0001] The present invention relates to compositions and their cured products, molded products, display devices, solid-state image sensors, and light guide plates. [Background technology]

[0002] In the field of optical instruments, high refractive index materials are in demand. By using high refractive index materials, lenses can be obtained, and these lenses can control the optical path within optical instruments. In solid-state image sensors, lenses are used to improve the light-gathering efficiency to each photoelectric conversion element. In display devices, lenses are used to improve the light extraction efficiency from pixels. Patent Document 1 discloses a composition containing a compound having a thiirane group or a thiethane group as a high refractive index material. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2024-035818 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, conventional compositions containing compounds with thiirane or thiethane groups may not have sufficient storage stability. Furthermore, cured products obtained from such compositions may yellow (deteriorate in color) in high-temperature environments, and improvements in these areas are needed.

[0005] Therefore, the main objective of the present invention is to provide a composition that can yield a cured product exhibiting a high refractive index and excellent resistance to yellowing, and further possesses good storage stability. [Means for solving the problem]

[0006] The present invention provides a composition described in [1] to [5], a molded article described in [6], a cured article described in [7], a display device described in [8], a solid-state imaging device described in [9], and a light guide plate described in

[10] . [1] A compound (A) having a thiirane group or a thietane group, an acid generator (B), and an amine compound (C) having a boiling point of 200 °C or higher, and a composition containing the same. [2] The composition according to [1], wherein the amine compound (C) contains a tertiary amine. [3] The composition according to [1] or [2], wherein the acid generator (B) contains a thermal acid generator. [4] The composition according to [3], wherein the thermal acid generator is at least one selected from the group consisting of iodonium salts and sulfonium salts. [5] The composition according to any one of [1] to [4], further containing an acid (D). [6] The composition according to any one of [1] to [5], wherein the compound (A) contains a compound represented by formula (II). [Chemical formula] [In formula (II), L 1x represents a single bond or a divalent group, and two Ls 1x may be the same or different. A 1x represents an oxygen atom or a sulfur atom, and two As 1x may be the same or different. However, at least one of the two As 1x is a sulfur atom. mx represents 0 or 1, and two mx may be the same or different. nx represents an integer from 0 to 6. R 1x represents a monovalent substituent, and when there are a plurality of Rs 1x and a plurality of Rs 1x may be the same or different. R 2xR represents a hydrogen atom or a monovalent substituent, and there are two R 2x They may be the same or different. A molded article obtained by curing any of the compositions described in [7][1] to [6]. A cured product of any of the compositions described in [8], [1], to [6]. A display device containing the cured product described in [9][8]. A solid-state image sensor comprising the cured material described in

[10] [8]. A light guide plate containing the cured material described in

[11] [8]. [Effects of the Invention]

[0007] The present invention provides a composition that can yield a cured product exhibiting a high refractive index and excellent resistance to yellowing, and furthermore, a composition having good storage stability. Some embodiments of the composition tend to exhibit excellent curability even when applied to acidic surfaces. The present invention also provides a molded article obtained by curing such a composition, a cured product of such a composition, a display device containing the cured product, a solid-state image sensor containing the cured product, and a light guide plate containing the cured product. [Modes for carrying out the invention]

[0008] Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.

[0009] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages within this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples.

[0010] In this specification, (meth)acrylate means acrylate or the corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl group and (meth)acrylic acid ester.

[0011] In this specification, unless otherwise specified, the materials exemplified below may be used individually or in combination of two or more, to the extent that the conditions are met. The content of each component refers to the total amount of multiple substances corresponding to each component, unless otherwise specified.

[0012] <Composition> The composition of one embodiment contains a compound (A) having a thiirane group or a thietan group (hereinafter sometimes referred to as "component (A)"), an acid generator (B) (hereinafter sometimes referred to as "component (B)"), and an amine compound (C) (hereinafter sometimes referred to as "component (C)"). The composition of this embodiment may further contain an acid (D) (hereinafter sometimes referred to as "component (D)"), an epoxy resin (E) having a structure represented by formula (e-1) (hereinafter sometimes referred to as "component (E)"), etc. According to the composition of this embodiment, it is possible to provide a cured product that exhibits a high refractive index and has excellent resistance to yellowing, and furthermore, has good storage stability. The composition of this embodiment tends to have excellent curing properties even when applied to an acidic surface.

[0013] (A) Component: Compound having a thiirane group or a thietan group (A) The composition of this embodiment contains component (A). Component (A) may be a curable compound. By containing component (A) in the composition, component (A) itself can polymerize to produce a cured product exhibiting a high refractive index.

[0014] Component (A) can be used without particular limitations as long as it is a compound having at least one thiirane group or thiethane group. Component (A) may be, for example, a compound having at least one group represented by formula (II-a), and preferably a compound having at least one group represented by formula (II-b).

[0015] [ka]

[0016] In formula (II-a), mx represents either 0 or 1. R 2x represents a hydrogen atom or a monovalent substituent. * indicates the connection position.

[0017] [ka]

[0018] In formula (II-b), L 1x This represents a single bond or a divalent group. mx represents either 0 or 1. R 2x represents a hydrogen atom or a monovalent substituent. * indicates the connection position.

[0019] L 1x Examples of divalent groups represented by include divalent aliphatic chain hydrocarbon groups which may have substituents; divalent alicyclic hydrocarbon groups which may have substituents; divalent aromatic hydrocarbon groups which may have substituents; and divalent groups which are combinations of these (e.g., aralkylene groups). The methylene group (-CH2-) included in the divalent group is -O-, -S-, -NR A -(R A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It may be substituted with -CO- or -SO2-.

[0020] Examples of divalent aliphatic chain hydrocarbon groups include saturated or unsaturated aliphatic chain hydrocarbon groups. More specifically, examples include methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl group, octanediyl group, nonanediyl group, decanediyl group, undecanediyl group, dodecanediyl group, tridecanediyl group, tetradecanediyl group, pentadecanediyl group, hexadecanediyl group, heptadecanediyl group, octadecanediyl group, nonadecanediyl group, eicosanediyl group, and other alkanediyl groups. Divalent aliphatic chain hydrocarbon groups may be linear or branched. The number of carbon atoms in a divalent aliphatic chain hydrocarbon group is usually 1 to 20, preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.

[0021] Examples of substituents that a divalent aliphatic chain hydrocarbon group may have include halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxyl groups; amino groups; acetyl groups; and cyano groups.

[0022] Examples of divalent alicyclic hydrocarbon groups include saturated or unsaturated alicyclic hydrocarbon groups. More specifically, monocyclic alicyclic hydrocarbon groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cyclooctanediyl, cyclononanediyl, and cyclodecanediyl groups; 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 groups. The number of carbon atoms in a 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.

[0023] Examples of substituents that a 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 groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; hydroxyl groups; amino groups; acetyl groups; and cyano groups.

[0024] The divalent aromatic hydrocarbon group may be monocyclic or polycyclic. Examples of divalent aromatic hydrocarbon groups include phenylene, naphthylene, anthracenediyl, and fluo-orangeyl groups. The number of carbon atoms in the divalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0025] Examples of substituents that a 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 groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; hydroxyl groups; amino groups; acetyl groups; and cyano groups.

[0026] R 2xThe monovalent substituents represented by include, for example, monovalent hydrocarbon groups such as optionally substituted monovalent aliphatic chain hydrocarbon groups, optionally substituted monovalent alicyclic hydrocarbon groups, optionally substituted monovalent aromatic hydrocarbon groups, and monovalent groups consisting of combinations thereof (e.g., aralkyl groups); hydroxyl groups; and groups substituted with one or two alkyl groups having 1 to 6 carbon atoms, such as amino groups, monomethylamino groups, monoethylamino groups, dimethylamino groups, diethylamino groups, and methylethylamino groups. Possible amino groups include: aliphatic heterocyclic groups with 4 to 20 carbon atoms such as pyrrolidinyl group, pyrrolidinyl group, imidazolidinyl group, imidazolinyl group, oxazolinyl group, thiazolyl group, piperidinyl group, morpholinyl group, piperazinyl group, indolyl group, isoindolyl group, quinolyl group, thienyl group, pyrrolyl group, furyl group, or heterocyclic groups with 3 to 20 carbon atoms such as aromatic heterocyclic groups; halogen atoms; nitro group; cyano group; carboxyl group; sulfo group; thiol group; formyl group; -SF3 group; and -SF5 group. Methylene groups (-CH2-) included in monovalent substituents are -O-, -S-, and -NR. B -(R B The ∫ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It may be substituted with -CO- or -SO2-. Examples of groups in which the methylene group (-CH2-) in a monovalent substituent is substituted with -O- include alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, and octyloxy groups; and alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, and methoxyethyl groups.

[0027] Examples of monovalent aliphatic hydrocarbon groups include saturated or unsaturated aliphatic hydrocarbon groups. More specifically, examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups. Monovalent aliphatic hydrocarbon groups may be linear or branched. The number of carbon atoms in a monovalent aliphatic hydrocarbon group is usually 1 to 20, preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.

[0028] Examples of substituents that a monovalent aliphatic chain hydrocarbon group may have include halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxyl groups; amino groups; acetyl groups; and cyano groups.

[0029] Examples of monovalent alicyclic hydrocarbon groups include saturated or unsaturated alicyclic hydrocarbon groups. More specifically, monocyclic alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl groups; 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 groups. The number of carbon atoms in a 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.

[0030] Examples of substituents that a 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 groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; hydroxyl groups; amino groups; acetyl groups; and cyano groups.

[0031] The monovalent aromatic hydrocarbon group may be monocyclic or polycyclic. Examples of monovalent aromatic hydrocarbon groups include phenyl, naphthyl, anthracenyl, and fluorenyl groups. The number of carbon atoms in the monovalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0032] Examples of substituents that a 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 groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; hydroxyl groups; amino groups; acetyl groups; and cyano groups.

[0033] mx represents either 0 or 1. When mx is 0, it represents a three-membered ring structure that is a thiirane group, and when mx is 1, it represents a four-membered ring structure that is a thietan group. mx is preferably 0.

[0034] Component (A) is preferably a compound containing an aromatic ring from the viewpoint of a high refractive index of the cured product. Examples of aromatic rings include aromatic hydrocarbon rings such as benzene rings, naphthalene rings, and anthracene rings; and aromatic heterocycles such as furan rings, pyrrole rings, benzofuran rings, thiophene rings, benzothiophene rings, indole rings, pyridine rings, quinoline rings, isoquinoline rings, pyridazine rings, pyrimidine rings, and triazine rings. The aromatic ring is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring.

[0035] Component (A) preferably includes a compound represented by formula (II) from the viewpoint of a high refractive index of the cured product.

[0036] [ka]

[0037] In formula (II), L 1x represents a single bond or a divalent group, and there are two L 1x They may be the same or different. A 1x represents an oxygen atom or a sulfur atom, and there are two A 1x They may be the same or different. However, if there are two A 1x At least one of them is a sulfur atom. mx represents either 0 or 1, and the two mx values ​​may be the same or different. nx represents an integer between 0 and 6. R 1x represents a monovalent substituent, R 1x If there are multiple R 1x They may be the same or different. R 2x R represents a hydrogen atom or a monovalent substituent, and there are two R 2x They may be the same or different.

[0038] In the compound represented by formula (II), the two groups represented by formula (II-c) may be bonded to any position between positions 1 and 8 of the naphthalene ring. The group represented by formula (II-c) on the naphthalene ring may be bonded to any two positions between positions 1 and 4 (or between positions 5 and 8), or to any one position between positions 1 and 4 (or between positions 5 and 8) and any one position between positions 5 and 8 (or between positions 1 and 4). Preferably, the group represented by formula (II-c) on the naphthalene ring is bonded to any one position between positions 1 and 4 (or between positions 5 and 8) and any one position between positions 5 and 8 (or between positions 1 and 4).

[0039] [ka]

[0040] In formula (II-c), L 1x , A 1x , mx, and R 2x The above has the same meaning as above, and * indicates the joining position.

[0041] R is a compound represented by formula (II) with one or more components. 1x If it has a monovalent substituent represented by R 1x The monovalent substituent represented by may be bonded to any position from 1 to 8 of the naphthalene ring, excluding the bonded position of the group represented by formula (II-c).

[0042] L 1x represents a single bond or a divalent group, and there are two L 1x They may be the same or different. In the compound represented by formula (II), there are two L 1x Preferably, at least one of the groups is an alkanediyl group, and more preferably, both are alkanediyl groups. In this case, the number of carbon atoms in the alkanediyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.

[0043] A 1x represents an oxygen atom or a sulfur atom, and there are two A 1x They may be the same or different. However, if there are two A 1x At least one of them is a sulfur atom. In the compound represented by formula (II), two A 1x Preferably, both are sulfur atoms. 1x As the number of sulfur atoms increases, it tends to be possible to obtain cured products that exhibit a higher refractive index and have superior solvent resistance.

[0044] mx represents either 0 or 1, and the two mx values ​​may be the same or different. In the compound represented by formula (II), the two mx values ​​are preferably both 0.

[0045] nx represents an integer from 0 to 6. Preferably, nx is an integer from 0 to 3, more preferably from 0 to 2, even more preferably 0 or 1, and particularly preferably 0.

[0046] R 1x represents a monovalent substituent, R 1x If there are multiple R 1x They may be the same or different. 1x As a monovalent substituent represented by , R 2x Examples of monovalent substituents similar to those represented by can be given.

[0047] R 2x R represents a hydrogen atom or a monovalent substituent, and there are two R 2x They may be the same or different. In the compound represented by formula (II), there are two R 2x Preferably, it is 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, even more 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.

[0048] (A) Examples of component (compound represented by formula (II)) include compounds represented by formula (II-A), formula (II-B), formula (II-C), formula (II-D), formula (II-E), and formula (II-F). L in formulas (II-A), (II-B), (II-C), (II-D), (II-E), and (II-F) 1x , A 1x ,mx,nx,R 1x , and R 2x This expresses the same meaning as above.

[0049] [ka]

[0050] In equations (II-A), (II-B), (II-C), (II-D), (II-E), and (II-F), there are two L 1x Preferably, at least one of the groups is an alkanediyl group, and more preferably, both are alkanediyl groups. In this case, the number of carbon atoms in the alkanediyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.

[0051] In formulas (II-A), (II-B), (II-C), (II-D), (II-E), and (II-F), the two mx values ​​are each independently 0 or 1, preferably 0.

[0052] In equations (II-A), (II-B), (II-C), (II-D), (II-E), and (II-F), nx is independently an integer from 0 to 6, preferably an integer from 0 to 3, more preferably an integer from 0 to 2, even more preferably 0 or 1, and particularly preferably 0.

[0053] In equations (II-A), (II-B), (II-C), (II-D), (II-E), and (II-F), there are two A 1x Each of these is independently either an oxygen atom or a sulfur atom. However, there are two A 1x At least one of them is a sulfur atom. 1x Preferably, both are sulfur atoms.

[0054] In equations (II-A), (II-B), (II-C), (II-D), (II-E), and (II-F), there are two R 2xEach of these is independently 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, even more 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. 2x They are preferably the same.

[0055] The following are specific examples of component (A) (compounds represented by formula (II)), but are not limited to these.

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] The molecular weight of component (A) (the compound represented by formula (II)) is preferably 2000 or less, more preferably 1000 or less, and even more preferably 750 or less, from the viewpoint of synthesis. The molecular weight of component (A) is preferably 50 or more, more preferably 100 or more, and even more preferably 150 or more, from the viewpoint of volatility.

[0073] (A) The compound represented by formula (II) as a component can be obtained by synthesizing the compound represented by formula (II-1) and reacting the compound represented by formula (II-1) with a sulfidating agent.

[0074] [ka]

[0075] In formula (II-1), L 1x ,mx,nx,R 1x , and R 2x This has the same meaning as equation (I) above.

[0076] The compound represented by formula (II-1) can be obtained, for example, by a method that includes a step of reacting the compound represented by formula (II-1a) with the compound represented by formula (II-1b).

[0077] [ka]

[0078] In equation (II-1a), nx and R 1x This expresses the same meaning as above.

[0079] [ka]

[0080] In formula (II-1b), L 1x , mx, and R 2x This has the same meaning as above, X 1X represents a leaving group.

[0081] The reaction between the compound represented by formula (II-1a) and the compound represented by formula (II-1b) can be carried out, for example, in the presence of a base. Examples of bases 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 t-butoxide, and potassium t-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-dimethylpyridine, 2,6-di-t-butylpyridine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, and tetramethylammonium chloride. The amount of base used may be, for example, 0.0001 to 10 moles per mole of the compound represented by formula (II-1a), preferably 0.001 to 5 moles, more preferably 0.01 to 4 moles, and even more preferably 0.1 to 3 moles.

[0082] Furthermore, two or more bases may be used in combination. When used in combination, it is preferable to use a combination of a carbonate such as sodium carbonate, potassium carbonate, lithium carbonate, or cesium carbonate, or a bicarbonate such as sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, or cesium bicarbonate, and a metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or cesium hydroxide, or a metal alkoxide such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium t-butoxide, or potassium t-butoxide, and it is more preferable to use a combination of a bicarbonate and a metal hydroxide. When used in combination, the two types may be added simultaneously or in stages.

[0083] In the compound represented by formula (II-1b), X 1X Examples of leaving groups represented by formula (II-1b) include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, trifluoromethylsulfonyl, perfluoroethylsulfonyl, perfluoropropylsulfonyl, and perfluorobutylsulfonyl; and arylsulfonyl groups such as phenylsulfonyl, p-toluenesulfonyl, p-fluorophenylsulfonyl, and pentafluorophenylsulfonyl. Specific examples of compounds represented by formula (II-1b) include epihalohydrin compounds (L 1x It is a methylene group, and mx is 0, R 2x Examples include compounds in which (I) is a hydrogen atom and X is a halogen atom. The amount of compound represented by formula (II-1b) used may be, for example, 0.01 to 20 moles, preferably 0.5 to 15 moles, per mole of the compound represented by formula (II-1a). In this step, the reaction may be carried out using two or more compounds represented by formula (II-1b).

[0084] The reaction between the compound represented by formula (II-1a) and the compound represented by formula (II-1b) is preferably carried out in a solvent. Examples of solvents include water, ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, alcohols, glimes, esters, aliphatic nitriles, sulfoxides, and amides. The following are examples of solvents:

[0085] 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. Aromatic hydrocarbons: benzene, toluene, xylene, mesitylene, naphthalene, anisole, nitrobenzene, aniline, tetralin, durene, etc. Halogenated aromatic hydrocarbons: Chlorobenzene, dichlorobenzene, chloronaphthalene, etc. Aliphatic hydrocarbons: pentane, hexane, heptane, etc. Aliphatic halogenated hydrocarbons: dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, tetrachloroethylene, etc. Ethers: Diethyl ether, diisopropyl ether, methyl t-butyl ether, cyclopentyl methyl ether, diphenyl ether, dimethoxyethane, dioxane, etc. Alcohols: methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, hexafluoroisopropanol, etc. Glymes: Methyl diglyme, ethyl diglyme, triglyme, diethylene glycol butyl methyl ether, etc. Esters: Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc. Aliphatic nitriles: Acetonitrile, etc. Sulfoxides: Dimethyl sulfoxide, sulfolane, etc. Amides: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0086] The reaction temperature between the compound represented by formula (II-1a) and the compound represented by formula (II-1b) may be, for example, -80 to 200°C, preferably -40 to 150°C, more preferably -20 to 120°C, and even more preferably -5 to 100°C.

[0087] In this way, the compound represented by formula (II-1) can be obtained. When the obtained compound represented by formula (II-1) is used in the synthesis of the compound represented by formula (II), the compound represented by formula (II-1) may be used after isolation, or it may be used as is without isolation.

[0088] The compound represented by formula (II) can be obtained, for example, by a method that includes a step of reacting the compound represented by formula (II-1) with a sulfurizing agent.

[0089] The reaction between the compound represented by formula (II-1) and a sulfurizing agent is a reaction in which the oxygen atom of the epoxy ring or oxetanyl ring of the compound represented by formula (II-1) is replaced with a sulfur atom using the sulfurizing agent, thereby forming a thiirane ring (episulfide ring) or thietane ring. Examples of sulfurizing agents include thiourea, methylthiourea, dimethylthiourea, trimethylthiourea, tetramethylthiourea, tetraethylthiourea, ethylenethiourea, phenylthiourea, diphenylthiourea, tolylthiourea, ditolylthiourea, sodium thiocyanate, potassium thiocyanate, etc. The amount of sulfurizing agent used can be arbitrarily adjusted according to the oxygen atom to be substituted. The amount of sulfurizing agent used is, for example, 0.01 to 20 moles, preferably 0.5 to 10 moles, per mole of the compound represented by formula (II-1). Furthermore, by adjusting the amount of sulfurizing agent used, the reaction temperature, the reaction time, etc., it is possible to replace both oxygen atoms in the compound represented by formula (II-1) with sulfur atoms, or to replace one of the oxygen atoms in the compound represented by formula (II-1) with a sulfur atom.

[0090] The reaction between the compound represented by formula (II-1) and the sulfiding agent is preferably carried out in a solvent. Examples of solvents include those similar to those exemplified in the reaction between the compound represented by formula (II-1a) and the compound represented by formula (II-1b). The reaction between the compound represented by formula (II-1) and the sulfiding agent may take place at, for example, -80 to 200°C, preferably -40 to 100°C, more preferably -20 to 80°C, and even more preferably -5 to 60°C.

[0091] A polymerization inhibitor may be added to the reaction system to suppress the polymerization of the compound represented by formula (II) that is produced. Examples of polymerization inhibitors include acids and acid anhydrides. More specifically, Inorganic acidic compounds such as nitric acid, hydrogen chloride (hydrochloric acid), perchloric acid, hypochlorous acid, chlorine dioxide, hydrofluoric acid, sulfuric acid, fuming sulfuric acid, sulfuryl chloride, boric acid, arsenic acid, arsenous acid, pyroaric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphorus oxychloride, phosphorus oxybromide, phosphorus sulfide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, hydrogen cyanide, chromic acid, anhydrous nitric acid, anhydrous sulfuric acid, boron oxide, arsenic acid pentoxide, phosphorus pentoxide, anhydrous chromic acid, silica, alumina, 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. 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, caprylic acid, naphthenic acid, methyl mercaptopropionate, malonic acid, glutaric acid, adipic acid, 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, benzyl acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, trifluoroacetic anhydride, and other organic carboxylic acids; Phosphates such as mono, di, and trimethyl phosphates, mono, di, and triethyl phosphates, mono, di, and triisobutyl phosphates, mono, di, and tributyl phosphates, mono, di, and trilauryl phosphates, and phosphites in which the phosphate portion thereof has been converted to a phosphite; Organophosphorus compounds such as dialkyldithiophosphates, exemplified by dimethyldithiophosphate; Phenols such as phenol, catechol, t-butylcatechol, 2,6-di-t-butylcresol, 2,6-di-t-butylethylphenol, resorcinol, hydroquinone, phloroglucin, pyrogallol, cresol, ethylphenol, butylphenol, nonylphenol, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, hydroxyphenylacetic acid amide, hydroxyphenylacetic acid methyl, hydroxyphenyl ethyl acetate, hydroxyphenethyl alcohol, hydroxyphenethylamine, hydroxybenzaldehyde, phenylphenol, bisphenol-A, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), bisphenol-F, bisphenol-S, α-naphthol, β-naphthol, aminophenol, chlorophenol, 2,4,6-trichlorophenol, and other phenols; Sulfonic acids such as 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, metanylic acid, sulfanilic acid, 4B-acid, diaminostilbenesulfonic acid, biphenylsulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, peric acid, laurentic acid, phenylJ acid, etc. These are some examples.

[0092] The amount of polymerization inhibitor used may be, for example, 0.0001 to 1.0 mole per mole of the compound represented by formula (II), preferably 0.001 to 0.5 moles, more preferably 0.01 to 0.25 moles, and even more preferably 0.05 to 0.15 moles. Among these, the polymerization inhibitor is preferably acetic acid, acetic anhydride, maleic acid, maleic anhydride, phosphoric acid, alkali metal hydrogen phosphate, or alkali metal dihydrogen phosphate.

[0093] The long-term stability of the compound represented by formula (II) obtained by washing the reaction product solution with an acidic aqueous solution can be improved. Specific examples of acids used in the acidic aqueous solution include those exemplified above as polymerization inhibitors. These acids may be used alone or in mixtures of two or more. The acidic aqueous solution generally tends to exhibit its effect at pH 6 or below, but the most effective range is pH 3 or below. The acids used in the acidic aqueous solution are preferably aqueous solutions of hydrogen chloride (hydrochloric acid), sulfuric acid, phosphoric acid, and / or maleic acid.

[0094] Furthermore, hydrogen sulfide adsorbents can be used to improve the stability of the compound represented by formula (II). Examples of hydrogen sulfide adsorbents include iron(III) hydroxide, zinc oxide, KNK-301 (zinc oxide-based adsorbent, manufactured by Kureha Oil & Fat Industry Co., Ltd.), Nionon 202A (iron oxide-based adsorbent, manufactured by Ibuki Shoji Co., Ltd.), and Limonic (iron hydroxide-based, manufactured by Nippon Limonite Co., Ltd.). The hydrogen sulfide adsorbent may be added during the reaction or added during the purification process after the reaction.

[0095] The content of the compound represented by formula (II) may be, for example, 50% by mass or more, 70% by mass or more, or 90% by mass or more, or 100% by mass, based on the total amount of component (A).

[0096] The content of component (A) may be, for example, 30 to 99% by mass, based on the total amount of solids in the composition, in order to easily obtain the effects of the present invention. The content of component (A) is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, preferably 98.5% by mass or less, more preferably 98% by mass or less, and even more preferably 97.5% by mass or less, based on the total amount of solids in the composition.

[0097] The total amount of solids in a composition refers to the sum of the components contained in the composition, excluding the solvent. The content of each component in the solids of a composition can be measured using known analytical methods such as liquid chromatography and gas chromatography. The content of each component in the solids of a composition may also be calculated from the formulation at the time of composition preparation.

[0098] (B) Ingredients: Acid generator (B) The composition of this embodiment contains component (B). Component (B) generates an acid upon irradiation with active energy rays and / or heat, which can promote the cationic polymerization of component (A).

[0099] Component (B) is a compound that can release a substance (acid) that initiates cationic polymerization by irradiation with active energy rays and / or heat. Component (B) is also called a cationic polymerization initiator. Examples of component (B) include diazonium salts (e.g., aromatic diazonium salts), sulfonium salts (e.g., aromatic diazonium salts, aliphatic sulfonium salts, etc.), iodonium salts (e.g., aromatic iodonium salts), pyridinium salts, cyclopentadienyl iron(II) complexes, etc. Depending on their structure, these can initiate cationic polymerization by irradiation with active energy rays and / or heat. Compounds that can release a substance (acid) that initiates cationic polymerization by irradiation with active energy rays are called photoacid generators or photocationic polymerization initiators. Compounds that can release a substance (acid) that initiates cationic polymerization by heat are also included in photoacid generators or photocationic polymerization initiators if they release a substance (acid) that initiates cationic polymerization by irradiation with active energy rays. Compounds that can release a substance (acid) that initiates cationic polymerization by heat are called thermal acid generators or thermal cationic polymerization initiators. Even compounds that can release substances (acids) that initiate cationic polymerization upon irradiation with active energy rays are included in the category of thermal acid generators or thermal cationic polymerization initiators if they release substances (acids) that initiate cationic polymerization upon heat.

[0100] Component (B) includes a thermal acid generator (thermal cationic polymerization initiator) from the viewpoint of improving the heat resistance of the composition and its cured product. The thermal acid generator (thermal cationic polymerization initiator) is preferably at least one selected from the group consisting of iodonium salts and sulfonium salts from the viewpoint of further improving the heat resistance of the composition and its cured product and further improving the storage stability of the composition.

[0101] The content of component (B) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the total amount of component (A) and other curable compounds, from the viewpoint of improving curability, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, from the viewpoint of improving the physical properties such as the mechanical properties of the cured product.

[0102] (C) Component: Amine compound with a boiling point of 200°C or higher (C) The composition of this embodiment contains component (C). By containing component (C), it is possible to prevent problems caused by component (B) in the composition during storage (for example, the progression of the hardening reaction due to acid release from component (B) during storage), thereby improving storage stability.

[0103] Examples of component (C) include primary amines, secondary amines, tertiary amines, polyamines, pyridines and pyridine derivatives, imidazoles and imidazole derivatives, pyrazoles and pyrazole derivatives, pyrazines and pyrazine derivatives, pyrimidines and pyrimidine derivatives. Component (C) preferably includes a tertiary amine, as it is likely to have a boiling point of 200°C or higher.

[0104] Examples of component (C) include dicyclohexylmethylamine (boiling point 265°C), tris(2-ethylhexyl)amine (boiling point 347°C), trybenzylamine (boiling point 390°C), trihexylamine (boiling point 265°C), triamylamine (boiling point 240°C), trioctylamine (boiling point 367°C), trinonylamine (boiling point 270°C / 1mmHg (0.1kPa)), tridecylamine (boiling point 430°C), and tributylamine (boiling point 217°C).

[0105] The boiling point (normal boiling point) of component (C) is 200°C or higher. When the boiling point of component (C) is 200°C or higher, the storage stability of the composition tends to improve. The boiling point of component (C) is preferably 220°C or higher, more preferably 240°C or higher, and even more preferably 260°C or higher. From the viewpoint of handling, the boiling point (normal boiling point) of component (C) is preferably 500°C or lower, more preferably 450°C or lower, and even more preferably 400°C or lower.

[0106] The molecular weight of component (C) is preferably 100 or more, more preferably 150 or more, and even more preferably 180 or more. The molecular weight of component (C) is preferably 500 or less, more preferably 450 or less, and even more preferably 400 or less.

[0107] The content of component (C) is preferably 0.1 parts by mass or more, more preferably 0.25 parts by mass or more, even more preferably 0.5 parts by mass or more, and particularly preferably 0.75 parts by mass or more, relative to 100 parts by mass of the total amount of component (A) and other curable compounds, from the viewpoint of improving curability and / or heat resistance, and preferably 10 parts by mass or less, more preferably 7 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, from the viewpoint of improving the physical properties such as the mechanical properties of the cured product.

[0108] (D) Component: Acid (D) The composition may further contain component (D). Component (D) may be a component that acts as a polymerization inhibitor. Component (D) may be added during the preparation of the composition or after the production of component (A). By containing component (D) in the composition, unintended polymerization of component (A) is suppressed, thereby improving the storage stability of the composition.

[0109] Component (D) can be exemplified by an acid similar to a polymerization inhibitor added to the reaction system to suppress the polymerization of the compound represented by formula (II) that is produced. Component (D) is preferably an organic carboxylic acid, more preferably an organic carboxylic acid having 10 or fewer carbon atoms, and even more preferably formic acid or acetic acid.

[0110] If the composition contains component (D), the content of component (D) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, particularly preferably 1 part by mass or more, preferably 100 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 25 parts by mass or less, particularly preferably 10 parts by mass or less, and most preferably 5 parts by mass or less, based on 100 parts by mass of the total amount of component (A).

[0111] (E) Component: Epoxy resin (E) having a structure represented by formula (e-1) The composition of this embodiment may further contain component (E). Component (E) is a resin having one or more epoxy groups (oxyranyl groups), preferably a resin having two or more epoxy groups (oxyranyl groups). Component (E) may be a curable resin. The composition tends to have good film-forming properties when it contains component (E).

[0112] [ka]

[0113] In formula (e-1), W 0 This represents a divalent group. * indicates the connection position.

[0114] W 0Examples of divalent groups represented by include divalent aliphatic chain hydrocarbon groups which may have substituents; divalent alicyclic hydrocarbon groups which may have substituents; divalent aromatic hydrocarbon groups which may have substituents; and divalent groups which are combinations of these (e.g., aralkylene groups). The methylene group (-CH2-) included in the divalent group is -O-, -CO-, -COO-, -SO2-, -NR C -(R C represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. The hydrocarbon group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms. ) or -CONH- may be substituted.

[0115] As for divalent aliphatic chain hydrocarbon groups, L 1x Examples of divalent groups similar to the divalent aliphatic chain hydrocarbon group represented by can be cited. The number of carbon atoms in the divalent aliphatic chain hydrocarbon group is usually 1 to 50, preferably 1 to 40, and more preferably 1 to 30.

[0116] As for divalent alicyclic hydrocarbon groups, L 1x Examples of divalent groups similar to alicyclic hydrocarbon groups can be given. The number of carbon atoms in a divalent alicyclic hydrocarbon group is usually 3 to 20, preferably 3 to 10, and more preferably 3 to 6.

[0117] As for divalent aromatic hydrocarbon groups, L 1x Examples of divalent groups similar to aromatic hydrocarbon groups can be given. The number of carbon atoms in a divalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0118] Examples of divalent groups consisting of a combination of a divalent aliphatic chain hydrocarbon group, a divalent aliphatic chain hydrocarbon group, and a divalent aromatic hydrocarbon group include the group represented by formula (x).

[0119] [ka]

[0120] In formula (x), W 1 and W 2 each independently represent a divalent cyclic hydrocarbon group which may have a monovalent substituent. R b1 and R b2 each independently represent a hydrogen atom or a monovalent hydrocarbon group. R b1 and R b2 may be bonded to each other to form a ring together with the carbon atoms to which they are respectively bonded. * represents the bonding position.

[0121] W 1 and W 2 Examples of the divalent cyclic hydrocarbon group which may have a monovalent substituent represented by include, for example, a divalent alicyclic hydrocarbon group which may have a monovalent substituent, a divalent aromatic hydrocarbon group which may have a monovalent substituent, and the like. The divalent cyclic hydrocarbon group which may have a monovalent substituent is preferably a divalent aromatic hydrocarbon group which may have a monovalent substituent, and more preferably a phenylene group which may have a monovalent substituent.

[0122] Examples of the divalent alicyclic hydrocarbon group include the same as those of the divalent alicyclic hydrocarbon group in the divalent group represented by L 1x .

[0123] Examples of the divalent aromatic hydrocarbon group include the same as those of the divalent aromatic hydrocarbon group in the divalent group represented by L 1x .

[0124] Examples of the monovalent substituent which the divalent cyclic hydrocarbon group, the divalent alicyclic hydrocarbon group, and the divalent aromatic hydrocarbon group may have include the same as those of the monovalent substituent represented by R 2x .

[0125] R b1 and R b2 Examples of the monovalent hydrocarbon group represented by include R 2xExamples of the monovalent hydrocarbon group in the monovalent substituent represented by the same as those.

[0126] R b1 and R b2 In, rings formed by bonding to each other and together with the carbon atoms to which each is bonded include, for example, hydrocarbon rings. Examples of the hydrocarbon ring include a ring formed from the carbon atom to which each of R b1 and R b2 is bonded, and a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include those similar to the divalent hydrocarbon group in the divalent group represented by L 1x In R b1 and R b2 the ring formed by bonding to each other and together with the carbon atoms to which each is bonded is preferably an alicyclic hydrocarbon ring formed from the carbon atom to which each of R b1 and R b2 is bonded, and a divalent aliphatic chain hydrocarbon group.

[0127] The epoxy resin having the structure represented by formula (e-1) is preferably an epoxy resin having the structure represented by formula (e-1x).

[0128]

Chemical formula

[0129] In formula (e-1x), W 1 , W 2 , R b1 , and R b2 are as defined above. * represents the bonding position.

[0130] (E) component can be obtained, for example, by reacting a compound represented by formula (e-1a) and a compound represented by formula (e-2a) by a conventionally known method to open the epoxy group of the compound represented by formula (e-2a). (E) component may be, for example, a polymer (reaction product) of a compound represented by formula (e-1a) and a compound represented by formula (e-2a).

[0131] [ka]

[0132] In formula (e-1a), W 0 This is synonymous with the above. In formula (e-2a), W 3 This represents a divalent group.

[0133] W 3 As a divalent group represented by , L 1x Examples of divalent groups similar to those represented by can be given.

[0134] The compound represented by formula (e-1a) is preferably the compound represented by formula (e-1b).

[0135] [ka]

[0136] In formula (e-1b), W 1 , W 2 , R b1 , and R b2 This is synonymous with the above.

[0137] The compound represented by formula (e-2a) is preferably the compound represented by formula (e-2b).

[0138] [ka]

[0139] In formula (e-2b), W 4 This represents a divalent hydrocarbon group.

[0140] As for divalent hydrocarbon groups, L 1xExamples of divalent hydrocarbon groups similar to those represented by the divalent group can be given. The divalent hydrocarbon group is preferably a divalent aliphatic chain hydrocarbon group which may have substituents.

[0141] The compound represented by formula (e-2b) can be obtained, for example, by reacting the compound represented by formula (ez) with an epihalohydrin using a conventionally known method.

[0142] [ka]

[0143] In formula (ez), W 4 This is synonymous with the above.

[0144] Component (E) can also be obtained, for example, by polycondensation of a compound represented by formula (e-1a) with an epihalohydrin.

[0145] (E)Specific examples of component include, for example, the jER® series (manufactured by Mitsubishi Chemical Corporation), the Epiclon® series (manufactured by DIC Corporation), and the Adeka Resin® EP series (manufactured by ADEKA Corporation).

[0146] The epoxy equivalent of component (E) is preferably 250 g / equivalent or more, more preferably 300 g / equivalent or more, even more preferably 350 g / equivalent or more, and particularly preferably 400 g / equivalent or more, from the viewpoint of film-forming properties. The epoxy equivalent of component (E) is preferably 15,000 g / equivalent or less, more preferably 12,000 g / equivalent or less, and even more preferably 10,000 g / equivalent or less.

[0147] The epoxy equivalent of component (E) can be measured, for example, by potentiometric titration in accordance with JIS K7236:2009. Alternatively, the epoxy equivalent of component (E) may be taken from, for example, the manufacturer's catalog value.

[0148] If the composition contains component (E), the content of component (E) may be, for example, 0.05 to 10% by mass, based on the total amount of solids in the composition, in order to easily obtain the effects of the present invention. The content of (E) is preferably 0.25% by mass or more, more preferably 0.5% by mass or more, even more preferably 0.75% by mass or more, particularly preferably 0.9% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 6% by mass or less, and particularly preferably 5% by mass or less, based on the total amount of solids in the composition.

[0149] solvent The composition of this embodiment may contain one or more solvents. Preferably, the solvent can dissolve or disperse component (A), and more preferably, it can dissolve or disperse other components other than component (A). Examples of solvents include the solvents exemplified in the reaction between the compound represented by formula (II-1a) and the compound represented by formula (II-1b) (organic solvents), ester solvents (solvents containing -COO- in the molecule but not -O-), ether solvents (solvents containing -O- in the molecule but not -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule but not -COO-), alcohol solvents (solvents containing OH in the molecule but not -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxides, and the like.

[0150] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0151] As ether solvents, 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, anisole, phenethole, methylanisole, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol ethyl methyl ether, ethylene glycol methylpropyl ether, ethylene glycol butyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene Dipropyl glycol ether, propylene glycol dibutyl ether, propylene glycol ethyl methyl ether, propylene glycol methyl propyl ether, propylene glycol butyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol methyl propyl ether, diethylene glycol butyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, dipropylene glycol ethyl methyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, triethylene glycol ethyl methyl ether,Examples include triethylene glycol methyl propyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dipropyl ether, tripropylene glycol dibutyl ether, tripropylene glycol ethyl methyl ether, tripropylene glycol methyl propyl ether, tripropylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol ethyl methyl ether, tetraethylene glycol methyl propyl ether, and tetraethylene glycol butyl methyl ether.

[0152] Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethyl ester ester Examples include ethyl toxic-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.

[0153] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0154] Examples of alcoholic solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0155] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0156] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0157] If the composition contains a solvent, the solvent content is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, preferably 1000 parts by mass or less, and more preferably 500 parts by mass or less, based on 100 parts by mass of the total solid content of the composition. If 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] Other components included in the composition include, for example, resins, curable compounds other than components (A) and (E), and additives. Examples of additives include inorganic particles, fillers, polymerization initiators, sensitizers, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, UV absorbers, antioxidants, and dispersants.

[0159] The composition of this embodiment may contain one or more resins. By including resins in the composition, it is possible to impart developability to the cured product of the composition, or to adjust the mechanical and / or optical properties of the cured product and the molded product containing it. Examples of resins include thermoplastic resins and curable resins. The curable resin may be a photocurable resin that hardens by irradiation with active energy rays, or a thermosetting resin that hardens by heat.

[0160] Examples of thermoplastic resins include olefin resins such as polyethylene resin, polypropylene resin, and polycycloolefin resin; (meth)acrylic resins such as poly(meth)acrylic acid ester resins; styrene resins such as polystyrene resin, styrene-acrylonitrile resin, and acrylonitrile-butadiene-styrene resin; vinyl resins such as polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol resin; polyester resins such as polyethylene terephthalate resin, polybutylene terephthalate resin, and liquid crystal polyester resin; polyacetal resin; polyamide resin; polycarbonate resin; polyurethane resin; and polyphenylene sulfide resin. One or more of these resins may be used as a polymer blend or polymer alloy.

[0161] Examples of curable resins include resins having photopolymerizable groups or thermopolymerizable groups. More specifically, examples include (meth)acrylic resins, epoxy resins, melamine resins, unsaturated polyester resins, phenolic resins, urea resins, alkyd resins, and polyimide resins.

[0162] Other examples of resins include alkali-soluble resins. The inclusion of an alkali-soluble resin in a composition can impart developability to the cured product of the composition. An alkali-soluble resin is a resin that is soluble in an alkaline aqueous solution. Specifically, examples include resins having carboxyl groups and / or phenolic hydroxyl groups.

[0163] The acid value of the alkali-soluble resin is preferably 10 to 170 mg KOH / g, more preferably 20 to 150 mg KOH / g, and even more preferably 30 to 140 mg KOH / g, from the viewpoint of improving the developability and solvent resistance of the cured product of the composition. The acid value is measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of alkali-soluble resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

[0164] Another example of a resin is a high refractive index resin. A high refractive index resin is a resin whose refractive index at a wavelength of 550 nm is 1.60 or higher.

[0165] The weight-average molecular weight (Mw) of the resin, measured by gel permeation chromatography (GPC) on a standard polystyrene basis, may be, for example, 5 to 2 million, preferably 10 to 1 million, and more preferably 15 to 750,000. The Mw of the resin can be adjusted by appropriately combining reaction conditions such as the selection of raw materials used, the preparation method, the reaction temperature, and the reaction time.

[0166] If the composition contains a resin, the resin content is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 80% by mass or less, and more preferably 70% by mass or less, based on the total amount of solids in the composition.

[0167] The composition of this embodiment may contain one or more curable compounds other than components (A) and (E). By including curable compounds other than components (A) and (E) in the composition, the viscosity or curability of the composition can be adjusted, and the mechanical and / or optical properties of the resulting cured product and the molded product containing it can be adjusted.

[0168] Examples of curable compounds other than components (A) and (E) include epoxy compounds other than components (A) and (E) (for example, alicyclic epoxy compounds having a structure in which alicyclic unsaturated hydrocarbons are epoxidized), oxetane compounds other than component (A), hydroxy compounds, vinyl ether compounds, allyl compounds, thiol compounds, polyphenol compounds, iso(thio)cyanate compounds, acid anhydrides, etc.

[0169] If the composition contains curable compounds other than components (A) and (E), the content of curable compounds other than components (A) and (E) is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 30% by mass or less, and more preferably 20% by mass or less, based on the total amount of solids in the composition.

[0170] <Cured products and molded products> The cured product of one embodiment is a cured product of the composition. The molded product of one embodiment is obtained by curing the composition and includes the cured product of the composition. The composition has excellent storage stability, resistance to yellowing, and curability on acidic surfaces, and can therefore be suitably used as a curable material for producing a cured product or a molded product containing the cured product. The cured product can preferably be obtained by curing components (A), (C), etc. in the composition by heat. The shape of the molded product containing the cured product is not particularly limited and may include film, plate, lens, powder, granules, non-spherical particles, crushed particles, porous, continuous mass, fibrous, tubular, hollow fiber, etc., and may be any shape depending on the intended use of the molded product.

[0171] The method for obtaining a molded product from the composition is not particularly limited and includes methods such as forming a film on a substrate and then molding it by etching, injection molding, and casting polymerization.

[0172] In the casting polymerization method, for example, the composition is injected into a molding mold, degassing is performed as needed, and then the mixture is cured by heating in an oven, and the resulting molded product is removed. The removed molded product can also be further cured by irradiation with active energy rays.

[0173] When forming a film as a molded product on a substrate, a composition is applied to the substrate, dried as necessary to form a coating film (coating layer), and the molded product, which is a cured film (cured layer), is obtained by curing the coating film (coating layer). The molded product may be a patterned cured film (cured layer). A patterned cured film can be obtained by patterning using methods such as photolithography, inkjet printing, or other printing methods. The patterning method may be, for example, photolithography. Photolithography is a method in which a composition is applied to a substrate, dried as necessary to form a coating film (coating layer), the coating film (coating layer) is exposed through a photomask, and the coating film (coating layer) after exposure is developed.

[0174] Examples of substrates include glass plates such as quartz glass, borosilicate glass, aluminasilate glass, soda-lime glass with a silica-coated surface, and alkali-free glass; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon (silicon wafers); and substrates on which thin films of aluminum, silver, or silver / copper / palladium alloys are formed. Methods for coating the composition onto the substrate include spin coating, slit coating, and slit-and-spin coating.

[0175] The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, from light with wavelengths in this range, light around 436 nm, 408 nm, or 365 nm may be selectively extracted using a bandpass filter, depending on the absorption wavelength of the photopolymerization initiator. Specific examples of light sources include mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc.

[0176] After pattern exposure, the exposed coating film (coating layer) may be heated (pre-development baked) before development.

[0177] Examples of developing solutions include aqueous solutions and solvents containing alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. As solvents, for example, solvents (organic solvents) exemplified by the reaction between the compound represented by formula (II-1a) and the compound represented by formula (II-1b), or the solvents mentioned above, can be used. The developing solution may also contain surfactants. Developing methods include the paddle method, dipping method, and spray method. Further heating (post-baking) may be performed on the patterned cured film (cured layer) obtained by development.

[0178] Since the cured product or molded product containing the same is formed from a composition, it can exhibit a high refractive index, and its refractive index can be controlled to a desired value by adjusting the composition of the composition, etc. The refractive index of the cured product or molded product containing the same at a wavelength of 550 nm may be 1.65 or higher, 1.68 or higher, 1.70 or higher, 1.72 or higher, 1.74 or higher, 1.75 or higher, or 1.76 or higher. The refractive index of the cured product or molded product containing the same at a wavelength of 550 nm may be, for example, 2.00 or lower, or 1.90 or lower.

[0179] The refractive index at a wavelength of 550 nm of a cured product or a molded product containing it 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 with a cured film. Next, the Δψ spectrum in the range of wavelengths from 400 nm to 800 nm is measured on the substrate with the cured film using an ellipsometer (JAWoollam, "M-2000"). The Δψ spectrum is then analyzed using the accompanying analysis software to determine the refractive index dispersion from 400 nm to 800 nm. The Cauchy model is applied as the analysis model. The refractive index at a wavelength of 550 nm is determined from the obtained refractive index dispersion. This allows the refractive index at a wavelength of 550 nm of the cured product or a molded product containing it to be determined.

[0180] <Usage> Applications of cured or molded products include, for example, glass substitutes and their surface coatings; coatings for window glass, daylighting glass, and light source protection glass in residences, facilities, and transportation equipment; window films for residences, facilities, and transportation equipment; interior and exterior materials and interior and exterior paints and coatings formed by said paints for residences, facilities, and transportation equipment; alkyd resin lacquer paints and coatings formed by said paints; acrylic lacquer paints and coatings formed by said paints; components for light sources that emit ultraviolet rays, such as fluorescent lamps and mercury lamps; shielding materials for electromagnetic waves generated from precision machinery, electronic and electrical equipment, and various displays; containers or packaging materials for food, chemicals, pharmaceuticals, etc.; bottles, boxes, blisters, cups, special packaging, compact disc coatings, agricultural and industrial sheets or film materials; anti-fading agents for printed materials, dyes, dyes, pigments, etc.; protective films for polymer supports (for example, for plastic parts of machinery and automobiles); printed materials Examples include overcoats; inkjet media coatings; laminated matte finishes; optical light films; safety glass / windshield intermediate layers; electrochromic / photochromic applications; overlaminate films; solar heat control films; cosmetics such as sunscreens, shampoos, conditioners, and hair styling products; textile products and fibers for clothing such as sportswear, stockings, and hats; household interior furnishings 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 (e.g., eyeglass lenses, camera lenses, and microlenses, pickup lenses, etc., described later), mirrors, and photographic materials; stationery such as mold films, transfer stickers, anti-graffiti films, tapes, and inks; signs, indicators, and their surface coating materials; substrates used in optical devices, etc.; optical waveguides; light guide plates; holograms; and LED encapsulants.

[0181] The cured or molded product is suitably used as a lens, which is an optical component used in optical instruments. Examples of optical instruments include solid-state image sensors and display devices. In solid-state image sensors, lenses are used to improve the light-gathering efficiency to each photoelectric conversion element. In display devices, lenses are used to improve the light extraction efficiency from pixels. The lenses may also be microlenses. Examples of display devices include liquid crystal displays and organic EL displays.

[0182] Inorganic compounds such as zirconium oxide and titanium oxide are conventionally known as high refractive index materials. However, when manufacturing molded products containing high refractive index materials made of inorganic compounds, molding can be difficult, such as difficulty in etching, and contamination problems can arise from the scattering of the high refractive index material during molding. These problems can be solved by using the high refractive index material of this embodiment, which is an organic compound.

[0183] The cured or molded product is suitably used as a light guide plate (LGP), which is an optical component for efficiently diffusing light. The light guide plate can be manufactured according to conventionally known methods in accordance with the standards required for light guide plates. For example, a plate-shaped light guide plate can be formed by injecting the composition of this embodiment between molds (which may be glass or metal) and curing it with heat, light, etc. Functional shapes can also be later imparted to the surface of the plate-shaped light guide plate by imprinting, inkjet printing, cutting, laser processing, photolithography, etching, etc. Optical elements such as diffraction gratings can also be laminated using adhesives or tacks. To form a dot pattern, the composition of this embodiment can be printed using an inkjet or the like, and then cured.

[0184] The cured product of the composition of this embodiment can be suitably used as a main-chain cleavage type positive resist. In the formation of a resist pattern using the cured product of the composition of this embodiment, upon irradiation with ionizing radiation or the like (for example, electron beam, KrF laser, ArF laser, EUV laser, etc.), the main chain of the polymer such as component (A), component (B), etc. constituting the cured product is cleaved in the irradiated portion of the resist film, resulting in a decrease in molecular weight. Therefore, a difference in solubility in the developer occurs between the exposed portion and the unexposed portion, and a resist pattern is formed. The resist pattern using the cured product of the composition of this embodiment can be applied when forming a resist pattern in the manufacture of printed circuit boards such as build-up substrates; semiconductors; photomasks; molds, etc.

Examples

[0185] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following, unless otherwise specified, "parts" means "parts by mass".

[0186] [Synthesis Example 1] [Synthesis of Compound (A-1)] ·Synthesis of Compound (A-1a) [Chemical Formula]

[0187] The inside of a four-necked flask equipped with a Dimroth condenser and a thermometer was made into a nitrogen atmosphere, 30 parts of 1,6-naphthalenedithiol, 165 parts of acetone, 45 parts of pure water, and 139 parts of epichlorohydrin were added to the flask, and the mixture was stirred in an ice bath for 15 minutes. Subsequently, 15 parts of sodium hydroxide, 66 parts of acetone, and 203 parts of pure water were added to another flask and completely dissolved, and then dropped into the above four-necked flask over 1 hour. After the dropping, 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 a compound represented by the formula (A-1a) (Compound (A-1a)).

[0188] 11H-NMR analysis and LC-MS measurements were performed to confirm the formation of compound (A-1a). 1 ¹H-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) LC-MS:[M+H] + =305.5

[0189] Synthesis of compound (A-1) [ka]

[0190] A four-necked flask equipped with a Liebig condenser and thermometer was placed under a nitrogen atmosphere. Three parts of compound (A-1a), 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 resulting mixture was purified to obtain 2.5 parts of compound (compound (A-1)) represented by formula (A-1).

[0191] 1 1H-NMR analysis and LC-MS measurements were performed to confirm the formation of compound (A-1). 1 ¹H-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) LC-MS:[M+H] + =337.5

[0192] [Examples 1-3 and Comparative Example 1] <Preparation of Composition> The components shown in Table 1 were placed in flasks in the amounts (in parts) shown in Table 1. Then, 81 parts of propylene glycol monomethyl ether acetate and 94 parts of cyclopentanone were added as solvents, and the mixture was stirred to prepare the liquid compositions of Examples 1-3 and Comparative Example 1. The compositions of Examples 1-3 and Comparative Example 1 were visually transparent, confirming that the components were uniformly dissolved.

[0193] The details of the abbreviations for the ingredients shown in Table 1 are as follows: (A) Component: Compound having a thiirane group or a thietan group (A) ·(A-1): Compound (A-1) (B) Ingredients: Acid generator (B) • (B-1): Iodonium salt type acid generator (IK-1FG (manufactured by Sunapro Co., Ltd.)) (C) Component: Amine compound with a boiling point of 200°C or higher (C) • (C-1): Dicyclohexylmethylamine (boiling point 265°C, molecular weight 195.4) • (C-2): Tris(2-ethylhexyl)amine (boiling point 347°C, molecular weight 353.7) • (C-3): Tribenzylamine (boiling point 390°C, molecular weight 287.4) (D) Component: Acid • (D-1): Formic acid

[0194] <Evaluation Test> (1) Formation of a hardened film Approximately 5 mL of each composition from Examples 1-3 and Comparative Example 1 was dropped onto a 4-inch diameter silicon wafer (0.5 mm thick, manufactured by Rokko Electronics Co., Ltd.), and a coated film was formed by spin-coating using a spin coater (Mikasa Corporation, "MS-B100") at 1000 rpm for 20 seconds. The silicon wafers with the coated films were heated at 60°C for 2 minutes to remove the solvent. Next, the silicon wafers with the coated films were heated at 120°C for 10 minutes as a post-bake to obtain silicon wafers with cured films. The film thickness of the cured films on the silicon wafers was measured using a stylus-type film thickness gauge (Bruker, "DekTak XT"), and the film thickness was 1.5 μm in all cases.

[0195] (2) Refractive index Regarding the silicon wafer with a cured film formed in (1) above, an ellipsometer (manufactured by J.A. Woolham, "M-2000") was used to measure the Δψ spectrum in the wavelength range from 400 nm to 800 nm. The Δψ spectrum was analyzed with the attached analysis software to obtain the refractive index dispersion in the wavelength range from 400 nm to 800 nm. The Cauchy model was applied to the analysis model. The refractive index at a wavelength of 550 nm among the obtained refractive index dispersions is shown in Table 1.

[0196] (3) Storage stability Using the compositions of Examples 1 to 3 and Comparative Example 1, the storage stability was evaluated based on the following evaluation criteria. First, the compositions of Examples 1 to 3 and Comparative Example 1 were each filled into brown bottles and stored in an environment at 40°C for 3 days. Next, using the compositions stored at 40°C for 3 days, a cured film was prepared in the same manner as in (1) above, and the film thickness of the prepared cured film was measured. Let the film thickness of the cured film prepared using the composition before storage at 40°C for 3 days be d1, and the film thickness of the cured film prepared using the composition after storage at 40°C for 3 days be d2. Based on the following formula, the film thickness change rate was calculated. Regarding the calculated film thickness change rate, the storage stability was evaluated according to the following evaluation criteria. The results are shown in Table 1. If the result is 3 or more, it can be said that the composition has little deterioration and good storage stability. Film thickness change rate = [(d2 / d1) - 1] × 100 [%] 5: The film thickness change rate was less than 1%. 4: The film thickness change rate was 1% or more and less than 3%. 3: The film thickness change rate was 3% or more and less than 5%. 2: The film thickness change rate was 5% or more and less than 10%. 1: The film thickness change rate was 10% or more.

[0197] (4) Yellowing resistance The yellowing resistance of the compositions of Examples 1-3 and Comparative Example 1 was evaluated. Using the silicon wafers with cured films prepared in (1) above, the yellowing resistance of the compositions (cured products) was evaluated according to the following evaluation criteria. Yellowing resistance was evaluated by placing the silicon wafers with cured films on a hot plate heated to 260°C for 5 minutes and calculating the change in transmittance of the cured film at a wavelength of 450 nm before and after heating (transmittance change = transmittance of the cured film before heating - transmittance of the cured film after heating). The results are shown in Table 1. If the result is 3 or higher, it can be said that the yellowing resistance is good. 5: The change in transmittance was between 0% and less than 5%. 4: The change in transmittance was between 5% and less than 10%. 3: The change in transmittance was between 10% and 12%. 2: The change in transmittance was between 12% and 15%. 1: The change in transmittance was 15% or more.

[0198] (5) Preparation of samples for evaluating hardening properties on acidic surfaces The curability on acidic surfaces was evaluated for the compositions of Examples 1-3 and Comparative Example 1. Polyacrylic acid (number average molecular weight 25,000) was dissolved in pure water to prepare a polyacrylic acid film-forming composition with a polyacrylic acid solid content of 20%. Approximately 3 mL of the above composition was dropped onto an alkali-free glass plate (0.7 mm thick, Corning, "Eagle XG"), and a coated film was formed by spin-coating using a spin coater (Mikasa Corporation, "MS-B100") at 1000 rpm for 20 seconds. The alkali-free glass plate with the coated film was heated at 100°C for 1 minute to remove moisture and obtain alkali-free glass with a polyacrylic acid film formed on it. The film thickness of the polyacrylic acid film on the alkali-free glass was measured using a stylus-type film thickness gauge (Bruker, "DekTak XT"), and the film thickness was found to be 1.5 μm. Next, following the same procedure as in (1) above, a coating film was formed on the polyacrylic acid film of the polyacrylic acid-coated glass plate. The alkali-free glass plate with the coating film formed on it was then heated at 60°C for 2 minutes to remove the solvent, thereby preparing a sample for curing evaluation.

[0199] (6) Evaluation of hardening properties on acidic surfaces The curability evaluation sample prepared in (5) above was heated at 120°C for 10 minutes as a post-bake. The curability of the composition (cured product) of the heated curability evaluation sample was evaluated according to the following criteria. The results are shown in Table 1. 5: No cracks or clouding were observed in the cured film, and no perforations were observed. 2: Two to five perforation defects were visually observed in the cured film. 1: Cracks and cloudiness were observed in the hardened film.

[0200] [Table 1]

[0201] As shown in Table 1, the compositions of the examples exhibited a high refractive index in the cured product and showed superior resistance to yellowing and storage stability compared to the compositions of the comparative examples. Furthermore, the compositions of the examples were found to exhibit excellent curability even when applied to acidic surfaces. These results confirm that the compositions of the present invention can provide cured products that exhibit a high refractive index and excellent resistance to yellowing, and also possess good storage stability.

Claims

1. Compound (A) having a thiirane group or a thiethane group, Acid generator (B), Amine compound (C) with a boiling point of 200°C or higher, A composition containing the following:

2. The composition according to claim 1, wherein the amine compound (C) comprises a tertiary amine.

3. The composition according to claim 1, wherein the acid generating agent (B) comprises a thermal acid generating agent.

4. The composition according to claim 3, wherein the thermal acid generating agent is at least one selected from the group consisting of iodonium salts and sulfonium salts.

5. The composition according to claim 1, further containing acid (D).

6. The composition according to claim 1, wherein the compound (A) comprises a compound represented by formula (II). 【Chemistry 1】 [In formula (II), L １ｘ represents a single bond or a divalent group, and there are two L １ｘ They may be the same or different. A １ｘ represents an oxygen atom or a sulfur atom, and there are two A １ｘ They may be the same or different. However, if there are two A １ｘ At least one of them is a sulfur atom. mx represents either 0 or 1, and the two mx values ​​may be the same or different. nx represents an integer between 0 and 6. R １ｘ represents a monovalent substituent, R １ｘ If there are multiple R １ｘ They may be the same or different. R ２ｘ represents a hydrogen atom or a monovalent substituent, and two R's ２ｘ may be the same or different. ]

7. A molded article obtained by curing the composition according to any one of claims 1 to 6.

8. A cured product of the composition according to any one of claims 1 to 6.

9. A display device comprising the cured product described in claim 8.

10. A solid-state image sensor comprising the cured product described in claim 8.

11. A light guide plate comprising the cured product described in claim 8.

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