Compositions and their cured products, molded products, display devices, and solid-state image sensors

Abstract

To provide a composition that can yield a cured product exhibiting a high refractive index and excellent resistance to yellowing, and further possessing 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 a triarylphosphine compound (C).

Description

[Technical Field]

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

[0002] High refractive index materials are in demand in the field of optical instruments. Lenses can be obtained from high refractive index materials, and lenses can be used to control the optical path within optical instruments. Lenses are used in solid-state image sensors to improve the light collection efficiency to each photoelectric conversion element, and in display devices to improve the light extraction efficiency from pixels. Conventionally, compositions containing compounds having thiirane groups or thiethane groups are known as high refractive index materials (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2024-035818 [Overview of the Initiative] [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 as described in [1] to [6], a molded article as described in [7], a cured article as described in [8], a display device as described in [9], and a solid-state imaging device as described in

[10] . [1] A compound (A) having a thiirane group or a thietane group, an acid generator (B), and a triarylphosphine compound (C), and a composition containing the same. [2] The composition according to [1], wherein the aryl group of the triarylphosphine compound (C) has an alkoxy group. [3] The composition according to [1] or [2], wherein the acid generator (B) is at least one selected from the group consisting of iodonium salts and sulfonium salts. [4] The composition according to any one of [1] to [3], further containing an acid (D). [5] The composition according to any one of [1] to [4], wherein the compound (A) includes a compound represented by formula (II). [Chemical formula] [In formula (II), L 1x , 1x , 2x , , , 2x , 1x , 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 , the plurality of Rs 1x may be the same or different. R 2x represents a hydrogen atom or a monovalent substituent, and two Rs 2x may be the same or different.] [6] The composition according to [2], wherein the alkoxy group is an alkoxy group having 1 to 3 carbon atoms. 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]. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a cured product that exhibits a high refractive index and excellent resistance to yellowing, and furthermore, a composition that has good storage stability. Some forms of the composition tend to exhibit excellent curability even when applied to acidic surfaces. Furthermore, according to the present invention, a molded product obtained by curing such a composition, a cured product of such a composition, a display device containing the cured product, and a solid-state image sensor containing the cured product are provided. [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 thiethane group (hereinafter sometimes referred to as "component (A)"), an acid generator (B) (hereinafter sometimes referred to as "component B"), and a triarylphosphine 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)"), 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 exhibit excellent curability 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 2xExamples of monovalent substituents represented by include 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; amino groups which may be 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; and pyrrolidine groups. Examples include aliphatic heterocyclic groups with 4 to 20 carbon atoms such as nyl groups, pyrrolinyl groups, imidazolidinyl groups, imidazolinyl groups, oxazolinyl groups, thiazolyl groups, piperidinyl groups, morpholinyl groups, piperazinyl groups, indolyl groups, isoindolyl groups, quinolyl groups, thienyl groups, pyrrolyl groups, and furyl groups, or heterocyclic groups with 3 to 20 carbon atoms such as aromatic heterocyclic groups; halogen atoms; nitro groups; cyano groups; carboxyl groups; sulfo groups; thiol groups; formyl groups; -SF3 groups; -SF5 groups; ethenyl (vinyl) groups; ethynyl groups; and -SO3Na groups. 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 8, even more preferably 1 to 6, particularly preferably 1 to 4, and most 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, fluorenyl, and pyrenyl 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, 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) is a compound that generates a substance (acid) that initiates cationic polymerization upon at least one of heat and / or active energy ray irradiation, and mainly promotes the cationic polymerization of component (A). Compounds that generate acid upon heat are called thermal acid generators. Compounds that generate acid upon irradiation with active energy rays are called photoacid generators. Some thermal acid generators also generate a substance (acid) that initiates cationic polymerization upon irradiation with active energy rays. Some photoacid generators also generate a substance (acid) that initiates cationic polymerization upon heat. Component (B) is either a thermal acid generator or a photoacid generator, and is preferably a thermal acid generator.

[0099] 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. When component (B) is an onium salt, the counter anion may be hexafluoroantimonate, hexafluorophosphate, P(F) x (Rf) 6-x - Examples include (Rf represents a perfluoroalkyl group, and x represents an integer from 1 to 5), tetrafluoroborate, and tetrakis(pentafluorophenyl)borate. Depending on their structure, these can initiate cationic polymerization with at least one of thermal and active energy ray irradiation. Among these, component (B) is preferably at least one selected from the group consisting of iodonium salts and sulfonium salts.

[0100] (B) Specific examples of component (B) include the TA-100 series, IK-1 series (both manufactured by Sunapro Co., Ltd.), SunAid SI series (manufactured by Sanshin Chemical Industry Co., Ltd.), and K-PURE CXC series (manufactured by King Industries).

[0101] The content of component (B) 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 curable compounds other than component (A), 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.

[0102] (C) Component: Triarylphosphine compound The composition of this embodiment contains component (C). In compositions containing components (A) and (B), applying component (C) tends to improve storage stability, enhance curability even when applied to acidic surfaces, and further improve the resistance of the cured product to yellowing. Component (C) may form a salt (phosphonium salt) with the acid. Forming a salt may improve the storage stability of the composition. The acid may be a Brønsted acid such as a carboxylic acid, sulfonic acid, or phenol, or a Lewis acid such as borane, aluminum, titanium, gallium, or indium.

[0103] Examples of the aryl group in component (C) include a phenyl group, naphthyl group, anthracenyl group, fluorenyl group, pyrenyl group, etc. The number of carbon atoms in the aryl group is usually 6 to 20, preferably 6 to 10. The aryl group is preferably a phenyl group. The three aryl groups in component (C) may be the same or different, preferably they are the same.

[0104] The aryl group of component (C) preferably has an alkoxy group. The presence of an alkoxy group in the aryl group tends to further improve the yellowing resistance of the cured product. The alkoxy group is preferably an alkoxy group having 1 to 3 carbon atoms. Examples of alkoxy groups having 1 to 3 carbon atoms include methoxy groups, ethoxy groups, and propoxy groups. The number of alkoxy groups in the aryl group may be, for example, 1 to 5, and is preferably 2 or more, more preferably 3 or more, for superior yellowing resistance, and preferably 4 or less, more preferably 3 or less, from the viewpoint of ease of synthesis. The number of alkoxy groups in the three aryl groups of component (C) is preferably the same for each.

[0105] Component (C) is preferably a compound represented by formula (C1).

[0106] [ka]

[0107] In formula (C1), x, y, and z each independently represent an integer between 0 and 5. R x , R y , and R z Each of these independently represents a monovalent hydrocarbon group, and R x , R y , and R z If there are multiple R x , R y , and R z These may be the same or different. cx, cy, and cz each independently represent an integer between 0 and 5, the sum of x and cx is less than or equal to 5, the sum of y and cy is less than or equal to 5, and the sum of z and cz is less than or equal to 5. R cx , R cy , and R cz Each of these independently represents a monovalent substituent, R cx , R cy , and R cz If there are multiple Rcx , R cy , and R cz may be the same or different from each other.

[0108] Since x, y, and z are excellent in yellowing resistance, they are preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and from the viewpoint of ease of synthesis, they are preferably 4 or less, more preferably 3 or less. x, y, and z are preferably the same from the viewpoint of ease of synthesis.

[0109] R x , R y , and R z Examples of the monovalent hydrocarbon group represented by R 2x are the same as those of the monovalent hydrocarbon group of the monovalent substituent represented by R C -(R C represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) may be substituted with -O-, -S-, -NR

[0110] R x , R y , and R z The monovalent hydrocarbon group represented by is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably an alkyl group having 1 or 2 carbon atoms. Examples of the alkyl group are the same as those of the alkyl group in the monovalent aliphatic chain hydrocarbon group which may have a substituent in the monovalent substituent represented by R 2x -(R C -(R C represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) may be substituted with -O-, -S-, -NR

[0111] R x , R y , and R z When there are a plurality of R x, R y , and R z From the viewpoint of ease of synthesis, these are preferably the same.

[0112] In the compound represented by formula (C1), -OR x , -OR y , and -OR z The -OR on the benzene ring may be bonded at any position from 2 to 6. x , -OR y , and -OR z Because it exhibits superior resistance to yellowing, it may be bound to any one of the positions 2 (ortho), 4 (para), and 6 (ortho), or to any two of the positions 2 (ortho), 4 (para), and 6 (ortho), or to all of the positions 2 (ortho), 4 (para), and 6 (ortho).

[0113] cx, cy, and cz are preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, particularly preferably 1 or less, and most preferably 0.

[0114] R cx , R cy , and R cz As a monovalent substituent represented by , R 2x Examples of monovalent substituents similar to those represented by R can be given. cx , R cy , and R cz If there are multiple R cx , R cy , and R cz From the viewpoint of ease of synthesis, these are preferably the same.

[0115] Component (C) is more preferably a compound represented by formula (C1-a).

[0116] [ka]

[0117] In equation (C1-a), x, y, z, R x , R y , and R z This expresses the same meaning as above.

[0118] The following are specific examples of component (C), but are not limited to these.

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] The content of component (C) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.2 parts by mass or more, and particularly preferably 0.3 parts by mass or more, relative to 100 parts by mass of the total amount of component (A) and curable compounds other than component (A), from the viewpoint of improving storage stability, curability, and resistance to yellowing, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, from the viewpoint of improving the physical properties such as the mechanical properties of the cured product.

[0127] (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.

[0128] 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.

[0129] 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).

[0130] solvent The composition 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] Examples of alcoholic solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0136] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0137] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0138] 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.

[0139] Other components included in the composition include, for example, resins, curable compounds other than component (A), 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.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] The composition of this embodiment may contain one or more curable compounds other than component (A). By including curable compounds other than component (A) 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.

[0149] Examples of curable compounds other than component (A) include epoxy compounds other than component (A), oxetane compounds other than component (A), hydroxy compounds, vinyl ether compounds, allyl compounds, thiol compounds, polyphenol compounds, iso(thio)cyanate compounds, acid anhydrides, and the like.

[0150] If the composition contains curable compounds other than component (A), the content of curable compounds other than component (A) 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.

[0151] <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 it. The cured product can preferably be obtained by curing component (A) 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.

[0152] 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.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] 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.

[0157] After pattern exposure, the exposed coating film (coating layer) may be heated (pre-development baked) before development.

[0158] 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.

[0159] 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, 1.76 or higher, or 1.78 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.

[0160] The refractive index at 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 silicon wafer, and the coating film is cured to obtain a silicon wafer with the cured film formed on it. Next, the Δψ spectrum in the range of 400 nm to 800 nm is measured on the silicon wafer with the cured film using an ellipsometer (JAWoollam, "M-2000"), and the Δψ spectrum is 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 550 nm is determined from the determined refractive index dispersion. This allows the refractive index at 550 nm of the cured product or a molded product containing it to be determined.

[0161] <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, dyed materials, dyes and pigments, etc.; protective films for polymer supports (for example, for plastic parts of machinery and automobile parts); printing Examples include: material 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; holograms; and LED encapsulants.

[0162] The molded product is suitably used as a lens, 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 light-emitting diode (EL) displays.

[0163] 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.

[0164] The cured product of the composition of this embodiment can be suitably used as a main-chain severing type positive resist. In forming a resist pattern using the cured product of the composition of this embodiment, irradiation with ionizing radiation (e.g., electron beam, KrF laser, ArF laser, EUV laser, etc.) severs the main chain of polymers such as component (A) that constitute the cured product in the irradiated area of ​​the resist film, resulting in a lower molecular weight. As a result, a difference in solubility in the developer occurs between the exposed and unexposed areas, and a resist pattern is formed. The resist pattern using the cured product of the composition of this embodiment can be applied when forming resist patterns in the manufacture of printed circuit boards such as build-up substrates, semiconductors, photomasks, molds, etc. [Examples]

[0165] The present invention will be described in more detail below 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".

[0166] [Synthesis Example 1] <Synthesis of compound (A-1)> Synthesis of compound (A-1a) [ka]

[0167] A four-necked flask equipped with a Liebig condenser and thermometer was placed under 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 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 dissolved completely. These were then added dropwise to the four-necked flask over 1 hour. After the dropwise addition, the temperature was raised to 30°C and stirred at 30°C for 2 hours. The resulting mixture was purified to obtain 46 parts of the compound represented by formula (A-1a) (compound (A-1a)).

[0168] 1 1H-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

[0169] Synthesis of compound (A-1) [ka]

[0170] 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).

[0171] 1 H-NMR analysis and LC-MS measurement were performed, and it was confirmed that compound (A-1) was formed. 1 H-NMR (heavy 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

[0172] [Examples 1 - 4 and Comparative Examples 1, 2] <Preparation of Composition> The compounding components shown in Table 1 were put into a flask with the addition amounts shown in Table 1 (unit: parts by mass). Further, as solvents, 81 parts by mass of propylene glycol monomethyl ether acetate and 94 parts by mass of cyclopentanone were added, and the liquid compositions of Examples 1 - 4 and Comparative Example 1 were prepared by stirring. The compositions of Examples 1 - 4 and Comparative Example 1 were visually transparent, and it was confirmed that the compounding components were uniformly dissolved.

[0173] The details of the abbreviations of the compounding components shown in Table 1 are as follows. Component (A): A compound having a thiirane group or a thietane group · (A-1): Compound (A-1) Component (B): An acid generator · (B-1): An iodonium salt type acid generator (IK-1FG (manufactured by San-Apro Ltd.)) Component (C): A triarylphosphine compound · (C-1): Triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) [Chemical formula] · (C-2): Tris(4-methoxyphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) [Chemical formula] ·(C-3): Tris(2,6-dimethoxyphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.)

Chemical formula

Chemical formula

[0174] <Evaluation test> (1) Formation of cured film About 5 mL of the compositions of Examples 1 to 4 and Comparative Example 1 were each dropped onto a 4-inch diameter silicon wafer (thickness 0.5 mm, manufactured by Rokukou Electronics Co., Ltd.), and spin-coated using a spin coater (manufactured by Mikasa Co., Ltd., "MS-B100") under the conditions of 1000 rpm and 20 seconds to form a coating film. The silicon wafer on which the coating film was formed was heated at 60°C for 2 minutes to remove the solvent. Next, the silicon wafer on which the coating film was formed was heated as a post-bake at 120°C for 10 minutes to obtain a silicon wafer on which a cured film was formed. When the film thickness of the cured film on the silicon wafer was measured with a stylus profilometer (manufactured by Bruker, "DekTak XT"), the film thickness was 1.5 μm in all cases.

[0175] (2) Refractive index Regarding the silicon wafer on which the cured film was formed, which was prepared in (1) above, a Δψ spectrum in the range from a wavelength of 400 nm to a wavelength of 800 nm was measured using an ellipsometer (manufactured by J.A. Woolham, "M-2000"), and the Δψ spectrum was analyzed with the attached analysis software to obtain the refractive index dispersion from a wavelength of 400 nm to a wavelength of 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.

[0176] (3) Storage stability The storage stability of the compositions of Examples 1-4 and Comparative Example 1 was evaluated based on the following evaluation criteria. First, the compositions of Examples 1-4 and Comparative Example 1 were each filled into brown bottles and stored at 40°C for 3 days. Next, cured films were prepared using the compositions stored at 40°C for 3 days in the same manner as in (1) above, and the film thickness of the prepared cured films was measured. The film thickness of the cured film prepared using the composition before storage at 40°C for 3 days was denoted as d1, and the film thickness of the cured film prepared using the composition after storage at 40°C for 3 days was denoted as d2. The rate of change in film thickness was calculated based on the following formula. The storage stability was evaluated based on the calculated rate of change in film thickness according to the following evaluation criteria. The results are shown in Table 1. If the result is 3 or higher, it can be said that the composition has not deteriorated much and has good storage stability. Film thickness change rate = [(d2 / d1)-1] × 100[%] 5: The rate of change in film thickness was less than 1%. 4: The rate of change in film thickness was 1% or more but less than 3%. 3: The rate of change in film thickness was 3% or more but less than 5%. 2: The rate of change in film thickness was 5% or more but less than 10%. 1: The rate of change in film thickness was 10% or more.

[0177] (4) Resistance to yellowing The yellowing resistance of the compositions of Examples 1-4 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 transmittance change was 15% or more.

[0178] (5) Preparation of samples for evaluating curability on an acidic surface For the compositions of Examples 1 to 4 and Comparative Example 1, the curability on an acidic surface was evaluated. Polyacrylic acid (number average molecular weight 25,000) was dissolved in pure water, and a composition for forming a polyacrylic acid film was adjusted so that the solid content of polyacrylic acid was 20%. Approximately 3 mL of the above composition was dropped onto an alkali-free glass plate (thickness 0.7 mm, manufactured by Corning, "Eagle XG"), and spin-coated using a spin coater (manufactured by Mikasa Co., Ltd., "MS-B100") under the conditions of 1000 rpm and 20 seconds to form a coating film. The alkali-free glass plate on which the coating film was formed was heated at 100 °C for 1 minute to remove moisture, and alkali-free glass on which a polyacrylic acid film was formed was obtained. When the film thickness of the polyacrylic acid film on the alkali-free glass was measured with a stylus profilometer (manufactured by Bruker, "DekTak XT"), the film thickness was 1.5 μm. Subsequently, in the same procedure as in (1) above, a coating film was formed on the polyacrylic acid film of the glass plate with a polyacrylic acid film, and the alkali-free glass plate on which the coating film was formed was heated at 60 °C for 2 minutes to remove the solvent, thereby preparing a sample for evaluating curability.

[0179] (6) Evaluation of curability on an acidic surface The sample for evaluating curability prepared in (5) above was heated as a post-bake at 120 °C for 10 minutes. After heating, the curability of the composition (cured product) of the sample for evaluating curability was evaluated according to the following criteria. The results are shown in Table 1. 5: No cracks and cloudiness were visually observed in the cured film, and no perforated defects were also visually observed. 2: Two or more and less than five perforated defects were visually observed in the cured film. 1: Cracks and cloudiness were visually observed in the cured film.

[0180]

Table 1

[0181] 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), Triarylphosphine compound (C) and A composition containing the following:

2. The composition according to claim 1, wherein the aryl group of the triarylphosphine compound (C) has an alkoxy group.

3. The composition according to claim 1, wherein the acid generating agent (B) is at least one selected from the group consisting of iodonium salts and sulfonium salts.

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

5. 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.]

6. The composition according to claim 2, wherein the alkoxy group is an alkoxy group having 1 to 3 carbon atoms.

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.

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