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

Abstract

To provide a composition that can give a cured product exhibiting a high refractive index and high adhesion, and further has good film-forming properties. 【Solution】A composition is provided that contains a compound (A) having a thiirane group or a thietane group and a compound (B) represented by the formula (B). JPEG2026069467000050.jpg38149 [In the formula, x, y, and z represent 1 to 5. R bz , bx , by , by , bz , bz , bx , by , R y , and R z represent a monovalent hydrocarbon group, and when there are a plurality of R x , R y , and R z , the plurality of R x , R y , and R z may be different from each other. bx, by, and bz represent 0 to 4, the sum of x and bx is 5 or less, the sum of y and by is 5 or less, and the sum of z and bz is 5 or less. R bx , R by , and R bz represent a monovalent substituent, and when there are a plurality of R bx , R by , and R bz , the plurality of R bx , R by , and R bz may be different from each other.]

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 having thiirane or thietan groups often exhibit insufficient film-forming properties (repellency and thickness unevenness) when applied to substrates, making it difficult to obtain good thin films.

[0005] Furthermore, while conventional compositions containing compounds having thiirane or thiethane groups tend to harden easily, their adhesion to the substrate (e.g., silicon wafer) may be reduced.

[0006] 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 high adhesion, and furthermore, has good film-forming properties. [Means for solving the problem]

[0007] 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], and a solid-state imaging device described in [9]. [1] A compound (A) having a thiirane group or a thietane group, a compound (B) represented by formula (B), and a composition containing the same. [Chemical formula] [In formula (B), x, y, and z each independently represent an integer of any one of 1 to 5. R , y , x , , z , R y , and R z each independently represent a monovalent hydrocarbon group, and when there are a plurality of R x , R y , and R z , the plurality of R x , R y , and R z may be the same or different from each other. bx, by, and bz each independently represent an integer of any one of 0 to 4, and the sum of x and bx is 5 or less, the sum of y and by is 5 or less, and the sum of z and bz is 5 or less. R bx , R s by , and R bz each independently represent a monovalent substituent, and when there are a plurality of R bx , R by , and R bz , the plurality of R bx , R by , and R bz may be the same or different from each other.] [2] The composition according to [1], wherein R x , R y , and R z are alkyl groups having 1 to 8 carbon atoms. [3] The composition according to [1] or [2], wherein x, y, and z are 2 or more. [4] The composition according to any one of [1] to [3], further containing acid (C). [5] The composition according to any one of [1] to [4], wherein the compound (A) comprises a compound represented by formula (II). [ka] [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. A molded article obtained by curing any of the compositions described in [6][1] to [5]. A cured product of any of the compositions described in [7], [1], or [5]. A display device containing the cured product described in [8][7]. A solid-state image sensor comprising the cured material described in [9][7]. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a cured product that exhibits a high refractive index and high adhesion, and furthermore, a composition having good film-forming properties. Compositions according to some embodiments tend to be excellent in terms of resistance to yellowing and transparency. 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]

[0009] Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.

[0010] 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.

[0011] 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.

[0012] 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.

[0013] <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)") and a compound (B) represented by formula (B) (hereinafter sometimes referred to as "component (B)"). The composition of this embodiment may further contain an acid (C) (hereinafter sometimes referred to as "component (C)"), etc. According to the composition of this embodiment, it is possible to provide a cured product that exhibits a high refractive index and high adhesion, and furthermore, has good film-forming properties. The composition of this embodiment also tends to be excellent in terms of resistance to yellowing and transparency.

[0014] (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.

[0015] 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).

[0016] [ka]

[0017] In formula (II-a), mx represents either 0 or 1. R 2x represents a hydrogen atom or a monovalent substituent. * indicates the connection position.

[0018] [ka]

[0019] In formula (II-b), L 1xThis 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.

[0020] 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-.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] R 2x The 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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, pyrrole, benzofuran, thiophene, benzothiophene, indole, pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, and triazine. The aromatic ring is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring.

[0036] Component (A) preferably includes a compound represented by formula (II) (hereinafter sometimes referred to as the "first compound") from the viewpoint of a high refractive index of the cured product.

[0037] [ka]

[0038] 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.

[0039] In the first compound, 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).

[0040] [ka]

[0041] 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.

[0042] The first compound has 1 or more R 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).

[0043] L 1x represents a single bond or a divalent group, and there are two L 1x They may be the same or different, or they may be the same. In the first compound, 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.

[0044] 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 first compound, there are 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.

[0045] mx represents either 0 or 1, and the two mx values ​​may be the same, different, or the same. In the first compound, the two mx values ​​are preferably both 0.

[0046] 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.

[0047] R 1x represents a monovalent substituent, R 1x If there are multiple R 1x They may be the same or different, or they may be the same. 1x As a monovalent substituent represented by , R 2x Examples of monovalent substituents similar to those represented by can be given.

[0048] R 2x R represents a hydrogen atom or a monovalent substituent, and there are two R 2x They may be the same or different, or they may be the same. In the first compound, 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.

[0049] Examples of the first compound include the compounds represented by 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.

[0050] [ka]

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] The following are specific examples of the first compound, but are not limited to these.

[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] [ka]

[0073] The molecular weight of the first compound 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.

[0074] The first compound 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.

[0075] [ka]

[0076] In formula (II-1), L 1x ,mx,nx,R 1x , and R 2x This has the same meaning as (Equation (II)) above.

[0077] 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).

[0078] [ka]

[0079] In equation (II-1a), nx and R 1x This expresses the same meaning as above.

[0080] [ka]

[0081] In formula (II-1b), L 1x , mx, and R 2x This has the same meaning as above, X 1x represents a leaving group.

[0082] 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.

[0083] In addition, two or more types of bases may be used in combination. When used in combination, carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, etc., or hydrogen carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, etc., and metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, etc., or metal alkoxides such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium t-butoxide, potassium t-butoxide, etc. are preferably combined, and a combination of a hydrogen carbonate and a metal hydroxide is more preferable. When used in combination, two types may be added simultaneously or may be added stepwise.

[0084] In the compound represented by formula (II-1b), X 1x Examples of the leaving group represented by include halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, trifluoromethylsulfonyl group, perfluoroethylsulfonyl group, perfluoropropylsulfonyl group, perfluorobutylsulfonyl group; arylsulfonyl groups such as phenylsulfonyl group, p-toluenesulfonyl group, p-fluorophenylsulfonyl group, pentafluorophenylsulfonyl group, etc. Specific examples of the compound represented by formula (II-1b) include epihalohydrin compounds (L 1x is a methylene group, mx is 0, R 2x is a hydrogen atom, and X 1x is a halogen atom). The amount of the compound represented by formula (II-1b) to be used may be, for example, 0.01 to 20 moles, preferably 0.5 to 15 moles, per 1 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).

[0085] 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:

[0086] 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.

[0087] 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.

[0088] 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 first compound, the compound represented by formula (II-1) may be used after isolation, or it may be used as is without isolation.

[0089] The first compound can be obtained, for example, by a method that includes the step of reacting a compound represented by formula (II-1) with a sulfidating agent.

[0090] 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.

[0091] 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 temperature between the compound represented by formula (II-1) and the sulfiding agent may be, 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.

[0092] A polymerization inhibitor may be added to the reaction system to suppress the polymerization of the first compound 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.

[0093] The amount of polymerization inhibitor used may be, for example, 0.0001 to 1.0 mole per mole of the first compound, 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.

[0094] The long-term stability of the first compound obtained can be improved by washing the reaction product solution with an acidic aqueous solution. 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 a mixture of two or more. The acidic aqueous solution usually exhibits 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.

[0095] Furthermore, a hydrogen sulfide adsorbent can be used to improve the stability of the first compound. 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.

[0096] The content of the first compound may be, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, based on the total amount of component (A), and may be 100% by mass or less, 98% by mass or less, 96% by mass or less, 94% by mass or less, 92% by mass or less, or 90% by mass or less.

[0097] Component (A) may further contain, in addition to the first compound, a compound having a thiirane group or a thiethane group other than the compound represented by formula (II) (hereinafter sometimes referred to as the "second compound"). When component (A) further contains the second compound in addition to the first compound, it tends to have even better film-forming properties and adhesion.

[0098] The second compound is not particularly limited as long as it is a compound having a thiirane group or a thiethane group other than the first compound (the compound represented by formula (II)). While the first compound is characterized by having a naphthalene ring that contributes to a high refractive index, the second compound is not limited thereto and may have a variety of skeletons such as a benzene ring, bisphenol skeleton, fluorene skeleton, novolac skeleton, etc.

[0099] The second compound is preferably a compound having at least one group represented by formula (III).

[0100] [ka]

[0101] In formula (III), L 1x , mx, and R 2x The above has the same meaning as above, and * indicates the joining position.

[0102] Examples of commercially available second compounds include TBIS(registered trademark)-AHSP (manufactured by Taoka Chemical Industries, Ltd.).

[0103] Specific examples of the second type of compound include, for example, the compounds represented by formulas (III-A), (III-B), and (III-C).

[0104] [ka]

[0105] [ka]

[0106] In formula (III-B), R represents a monovalent aliphatic chain hydrocarbon group which may have substituents. n represents an integer between 1 and 10.

[0107] A monovalent aliphatic chain hydrocarbon group which may have substituents represented by R is, for example, R 2x Examples of monovalent aliphatic chain hydrocarbon groups that may have a monovalent substituent represented by can be cited.

[0108] [ka]

[0109] Other examples of the second type of compound include, for example, the following compounds:

[0110] [ka]

[0111] The content of the second compound may be, for example, 0% by mass or more, 2% by mass or more, 4% by mass or more, 6% by mass or more, 8% by mass or more, or 10% by mass or more, based on the total amount of component (A), and may be 50% by mass or less, 40% by mass or less, 30% by mass or less, or 20% by mass or less.

[0112] The content of component (A) may be, for example, 30 to 99.9% 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 99.5% by mass or less, more preferably 99% by mass or less, and even more preferably 98.5% by mass or less, based on the total amount of solids in the composition.

[0113] The total amount of solid content in the composition means the total of the components contained in the composition excluding the solvent. The content of each component in the solid content of the composition can be measured by known analytical means such as liquid chromatography and gas chromatography. The content of each component in the solid content of the composition may also be calculated from the formulation at the time of preparing the composition.

[0114] (B) Component: Compound (B) represented by formula (B) The composition of this embodiment contains the (B) component. By containing the (B) component in the composition, it is possible to obtain a cured product showing high adhesion, and the film-forming property tends to be good. The (B) component may form a salt (phosphonium salt) together with an acid. The storage stability of the composition may be improved by forming a salt. The acid may be a Bronsted acid such as carboxylic acid, sulfonic acid, phenol, etc., or a Lewis acid such as borane, aluminum, titanium, gallium, indium, etc.

[0115]

Chemical formula

[0116] In formula (B), x, y, and z each independently represent an integer of 1 to 5. R x , R y , and R z each independently represent a monovalent hydrocarbon group, and when there are a plurality of R x , R y , and R z , the plurality of R x , R y , and R z may be the same or different from each other. <000]] bx, by, and bz each independently represent an integer of 0 to 4, and the sum of x and bx is 5 or less, the sum of y and by is 5 or less, and the sum of z and bz is 5 or less. R bx , R by , and R bzEach of these independently represents a monovalent substituent, R bx , R by , and R bz If there are multiple R bx , R by , and R bz These may be the same or different.

[0117] x, y, and z are preferably 2 or more, more preferably 3 or more, because they offer superior resistance to yellowing, and preferably 4 or less, more preferably 3 or less, from the viewpoint of ease of synthesis. From the viewpoint of ease of synthesis, x, y, and z are preferably the same.

[0118] R x , R y , and R z As a monovalent hydrocarbon group represented by R, 2x Examples of monovalent hydrocarbon groups similar to the monovalent substituents represented by can be found. The methylene group (-CH2-) contained in the monovalent hydrocarbon group is -O-, -S-, -NR C -(R C represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It may be substituted with -CO- or -SO2-.

[0119] 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, even more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably an alkyl group having 1 or 2 carbon atoms. As for alkyl groups, R 2x Examples of alkyl groups in monovalent aliphatic chain hydrocarbon groups that may have substituents, as represented by , can be found. The methylene group (-CH2-) included in the alkyl group is -O-, -S-, -NR C -(R C represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It may be substituted with -CO- or -SO2-.

[0120] Rx , R y , and R z If there are multiple R x , R y , and R z From the viewpoint of ease of synthesis, these are preferably the same.

[0121] In the compound represented by formula (B), -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).

[0122] bx, by, and bz are preferably 3 or less, more preferably 2 or less, even more preferably 1 or less, and particularly preferably 0.

[0123] R bx , R by , and R bz As a monovalent substituent represented by , R 2x Examples of monovalent substituents similar to those represented by R can be given. bx , R by , and R bz If there are multiple R bx , R by , and R bz From the viewpoint of ease of synthesis, these are preferably the same.

[0124] Component (B) is preferably a compound represented by formula (Ba).

[0125] [ka]

[0126] In equation (Ba), x, y, z, R x , R y , and R z This expresses the same meaning as above.

[0127] The following are specific examples of component (B) (compounds represented by formula (B)), but are not limited to these.

[0128] [ka]

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] 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, heat resistance, adhesion, and film-forming properties, and preferably 10 parts by mass or less, more preferably 7.5 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.

[0133] (C) Component: Acid (C) The composition may further contain component (C). Component (C) may be a component that acts as a polymerization inhibitor. Component (C) may be added during the preparation of the composition or after the production of component (A). By containing component (C) in the composition, unintended polymerization of component (A) is suppressed, thereby improving the storage stability of the composition.

[0134] Component (C) is similar to an acid used as a polymerization inhibitor added to the reaction system to suppress the polymerization of the compound represented by formula (II) that is produced. Component (C) 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.

[0135] If the composition contains component (C), the amount of component (C) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 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).

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] Examples of alcoholic solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0142] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0143] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0144] 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.

[0145] 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.

[0146] (resin) The composition may contain one or more resins. The inclusion of resins in the composition makes it 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 / or molded product containing it. Examples of resins include thermoplastic resins and curable resins. The curable resin may be a photocurable resin that hardens upon irradiation with active energy rays, or a thermosetting resin that hardens upon heat.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] (Curable compounds other than component (A)) The composition may contain one or more curable compounds other than component (A). By including curable compounds other than component (A), 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.

[0155] 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.

[0156] 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.

[0157] <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 made by curing the composition and includes the cured product of the composition. Because the composition has excellent film-forming properties, adhesion, curability, etc., it can be suitably used as a curable material for making a cured product or a molded product containing the cured product. 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-like, plate-like, lens-like, powder-like, granular, non-spherical particulate, crushed particulate, porous, continuous mass, fibrous, tubular, hollow fiber-like, etc., and may be any shape depending on the intended use of the molded product.

[0158] When forming a cured film as a molded product on a substrate, the composition is applied to the substrate, and volatile components such as solvents are removed by heating and drying (pre-baking) and / or vacuum drying to form a coating film, and the cured film can be obtained by curing the coating film.

[0159] Examples of substrates include glass plates such as quartz glass, borosilicate glass, aluminasilate glass, and soda-lime glass with a silica coating on the surface; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon substrates; and substrates on which thin films of aluminum, silver, silver / copper / palladium alloy, etc., are formed. Other cured films, resin films, transistors, circuits, etc., may be formed on these substrates.

[0160] Methods for applying the composition include spin coating, slit coating, and slit and spin coating.

[0161] When performing heat drying (pre-baking), the heating temperature is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When performing vacuum drying, it is preferable to do so under a pressure of 50 to 150 Pa and at a temperature in the range of 20 to 25°C.

[0162] The thickness of the coated film is not particularly limited and can be appropriately selected according to the desired thickness of the cured film.

[0163] Next, the coating film is cured. The coating film may be cured by heating (post-bake) or light irradiation, and heating is preferred. The heating temperature is preferably 60 to 250°C, more preferably 80 to 235°C, even more preferably 80 to 180°C, and particularly preferably 80 to 150°C. The heating time is preferably 1 minute to 72 hours, more preferably 10 minutes to 48 hours.

[0164] The thickness of the cured film is not particularly limited and can be adjusted as appropriate depending on the purpose and application. The thickness of the cured film may be, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

[0165] 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.

[0166] 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.

[0167] <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 coating films formed by said paints for residences, facilities, and transportation equipment; alkyd resin lacquer paints and coating films formed by said paints; acrylic lacquer paints and coating films formed by said paints; components for ultraviolet light sources 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); Examples include: overcoats for printed materials; inkjet media coatings; matte laminates; optical light films; intermediate layers for safety glass / windshields; 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.

[0168] The molded article is suitably used as a lens, which is an optical product used in optical devices. Examples of optical devices include solid-state imaging devices, display devices, and the like. In a solid-state imaging device, a lens is used for the purpose of improving the light condensing efficiency for each photoelectric conversion element. In a display device, a lens is used for the purpose of improving the light extraction efficiency from pixels. The lens may be a microlens. Examples of display devices include liquid crystal display devices, organic EL display devices, and the like.

[0169] As high refractive index materials, inorganic compounds such as zirconium oxide and titanium oxide have been conventionally known. However, when producing a molded article containing a high refractive index material composed of an inorganic compound, molding may not be easy, such as difficulty in the progress of etching, and there may be a problem of contamination due to the scattering of the high refractive index material during molding. Such problems can be solved by using the high refractive material of the present embodiment, which is an organic compound.

[0170] The cured product of the composition of the present 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 the present 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 the present embodiment can be applied when forming a resist pattern in the manufacture of printed boards such as build-up boards; semiconductors; photomasks; molds, etc.

Examples

[0171] 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".

[0172] [Synthesis Example 1] <Synthesis of compound (A-1)> Synthesis of compound (A-1a) [ka]

[0173] 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)).

[0174] 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

[0175] Synthesis of compound (A-1) [ka]

[0176] 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).

[0177] 1 H-NMR analysis and LC-MS measurement were performed, and it was confirmed that compound (A-1) was produced. 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

[0178] [Synthesis Example 2] [Synthesis of Compound (III-A)] Compound (III-A) was synthesized according to the method described in JP-A-2024-175660. [Chemical Formula]

[0179] [Synthesis Example 3] [Synthesis of Compound (III-B)] Compound (III-B) was synthesized according to the method described in JP-A-2024-035817. In formula (III-B), R represents a methyl group and n represents an integer of 1 to 10. <000​​​​​​​​​​​​​​​​​​​​​​​<Preparation of composition> The components shown in Table 1 were placed in flasks in the amounts (unit: parts by mass) shown in Table 1. Furthermore, 81 parts by mass of propylene glycol monomethyl ether acetate and 94 parts by mass of cyclopentanone were added as solvents, and the mixture was stirred to prepare the liquid compositions of Examples 1-8 and Comparative Examples 1 and 2. The compositions of Examples 1-8 and Comparative Examples 1 and 2 were observed to be transparent, confirming that the components were uniformly dissolved.

[0182] The details of the abbreviations for the ingredients shown in Table 1 are as follows: (A) Component: Compound having a thiirane group or a thiethane group • First compound (A1) (A1-1): Compound (A-1) • Second compound (A2) (A2-1): TBIS(registered trademark)-AHSP (manufactured by Taoka Chemical Industry Co., Ltd.) (A2-2): Compound (III-A) (A2-3): Compound (III-B) (A2-4): Compound (III-C) (B) Component: Compound represented by formula (B) • (B-1): Tris(2,4,6-trimethoxyphenyl)phosphine (manufactured by Sigma-Aldrich) [ka] • (B-2): Tris(4-methoxyphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) [ka] • (B-3): Tris(2-methoxyphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) [ka] • (B-4): Tris(2,6-dimethoxyphenyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) [ka] (b1) Components: Thermobase generators other than component (B) • (b1-1): Ammonium (DBU) salt type thermobase generator (U-CAT SA102 (manufactured by Sunapro Co., Ltd.)) (b2) Ingredients: Heat acid generator • (b2-1): Sulfonium salt type thermal acid generator (TA-100FG (manufactured by Sunapro Co., Ltd.)) (C) Component: acid • (C-1): Formic acid

[0183] <Evaluation Test> (1) Formation of a hardened film Approximately 5 mL of each composition from Examples 1-8 and Comparative Examples 1 and 2 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.

[0184] (2) Refractive index For the silicon wafers with the cured film prepared in (1) above, the Δψ spectrum in the wavelength range from 400 nm to 800 nm was measured using an ellipsometer (JAWoollam, "M-2000"), and the refractive index dispersion in the wavelength range from 400 nm to 800 nm was determined by analyzing the Δψ spectrum with the accompanying analysis software. The Cauchy model was applied as the analysis model. The refractive index at a wavelength of 550 nm among the determined refractive index dispersions is shown in Table 1.

[0185] (3) Film formability The silicon wafer with the coated film formed after the solvent was removed, as described in (1) above, was used as the sample. The coated film of the sample was observed, and the film-forming properties of the composition were evaluated according to the following evaluation criteria. The results are shown in Table 1. A perforation defect means that a hole of 1 mm or more in diameter is formed in the coated film, exposing the surface of the silicon wafer. A repellent defect means that although no exposed area is observed on the silicon wafer, the film thickness is partially thinned, mainly around environmental foreign matter, resulting in crater-like defects of less than 1 mm in diameter. A result of 5 or higher indicates good film-forming properties. 6. No hole defects or puncture defects were observed. 5: One to three splatter defects were observed. 4: Between 3 and 7 jack defects were observed. 3: One to three perforated defects were observed. 2: Three or more hole defects were observed, or seven or more puncture defects were observed. 1: Whitening was observed in the coated film.

[0186] (4) Adhesion The silicon wafer with the cured film prepared in (1) above was used as the sample. The cured film of the sample was peeled off with a carving knife, partially exposing the surface of the silicon wafer. The exposed area was shaped like a cross. At this time, it was confirmed that the silicon wafer in the exposed area was not abraded. Next, air blowing was performed near the exposed area of ​​the silicon wafer, and the adhesion was evaluated by visually checking the condition of the sample before and after air blowing. Air blowing means blowing compressed air onto the sample surface. Air blowing was performed under the following conditions: pressure when closed 0.5 MPa, nozzle diameter 1 mm, angle between nozzle and sample 20°, distance between nozzle and sample 3 cm, and blowing time 5 seconds. The results are shown in Table 1. If the result is 5 or higher, it can be said that the adhesion is good. 6: No change was observed in the sample. 5: The area of ​​partial peeling of the hardened film of the sample caused by the engraving tool expanded slightly. 1: The area of ​​partial delamination caused by the engraving tool on the hardened film of the sample expanded significantly.

[0187] (5) Resistance to yellowing The yellowing resistance was evaluated for Examples 1-8 and Comparative Examples 1 and 2. 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. 6: The change in transmittance was between 0% and less than 3%. 5: The change in transmittance was between 3% and 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.

[0188] [Table 1]

[0189] As shown in Table 1, the compositions of the examples exhibited a high refractive index in the cured product and had excellent film-forming properties and adhesion. In contrast, the compositions of the comparative examples lacked sufficient film-forming properties or adhesion. These results confirm that the compositions of the present invention can provide cured products exhibiting a high refractive index and high adhesion, and furthermore, have good film-forming properties.

Claims

1. Compound (A) having a thiirane group or a thiethane group, Compound (B) represented by formula (B), A composition containing the following: 【Chemistry 1】 [In formula (B), x, y, and z each independently represent an integer between 1 and 5. R ｘ 、 R ｙ 、 and R ｚ each independently represents a monovalent hydrocarbon group, and when there are a plurality of R ｘ 、 R ｙ 、 and R ｚ 、 the plurality of R ｘ 、 R ｙ 、 and R ｚ may be the same or different from each other. bx, by, and bz each independently represent an integer between 0 and 4, the sum of x and bx is 5 or less, the sum of y and by is 5 or less, and the sum of z and bz is 5 or less. R ｂｘ , R ｂｙ , and R ｂｚ Each of these independently represents a monovalent substituent, R ｂｘ , R ｂｙ , and R ｂｚ If there are multiple R ｂｘ , R ｂｙ , and R ｂｚ These may be the same or different.

2. R ｘ , R ｙ , and R ｚ The composition according to claim 1, wherein the alkyl group has 1 to 8 carbon atoms.

3. The composition according to claim 1, wherein x, y, and z are 2 or more.

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

5. The composition according to claim 1, wherein the compound (A) comprises a compound represented by formula (II). 【Chemistry 2】 [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.

6. A molded article obtained by curing the composition according to any one of claims 1 to 5.

7. A cured product of the composition according to any one of claims 1 to 5.

8. A display device comprising the cured product described in claim 7.

9. A solid-state image sensor comprising the cured product described in claim 7.

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