Composition and its cured product, molded article, display device, and solid-state imaging element

Abstract

To provide a composition containing a compound having at least one thiirane or thietane group, where the composition can produce a cured product with excellent yellowing resistance.SOLUTION: A composition comprises a compound represented by formula (I-1) or formula (I-2), and a compound having at least one thiirane or thietane group. In formula (I-1), R1 and R2 each independently represent a monovalent substituent. In formula (I-2), R3 and R4 each independently represent a monovalent substituent, and L1 represents a divalent group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition, a cured product thereof, a molded product, a display device, and a solid-state imaging device. [Background technology]

[0002] Highly refractive index materials are in demand in the field of optical equipment. Highly refractive index materials can be used to obtain lenses, which can control the optical path within optical equipment. Lenses are used in solid-state imaging devices to improve the light-collection efficiency of each photoelectric conversion element, and in display devices to improve the light extraction efficiency from pixels. Various highly refractive index materials have been developed to date (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2023 / 058449 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have conducted research into high refractive index materials and found that compounds containing at least one thiirane or thietane group are useful as high refractive index materials. However, cured products of compositions containing such compounds may yellow (deteriorate in color) in high temperature environments, and there is still room for improvement.

[0005] Therefore, a main object of the present invention is to provide a composition containing a compound having at least one thiirane group or thietane group, which is capable of giving a cured product having excellent yellowing resistance. [Means for solving the problem]

[0006] The present invention provides the composition according to any one of [1] to [6], the molded product according to [7], the cured product according to [8], the display device according to [9], and the solid-state imaging device according to

[10] . [1] A composition containing a compound represented by formula (I-1) or formula (I-2) and a compound having at least one thiirane group or thietane group. [ka] [In formula (I-1), R 1 and R 2 each independently represents a monovalent substituent. [ka] [In formula (I-2), R 3 and R 4 each independently represents a monovalent substituent. L 1 represents a divalent group. [2] R 1 and the above R 2 and at least one of the above R 3 and the above R 4 The composition according to [1], wherein at least one of the above is a monovalent aromatic hydrocarbon group which may have a substituent. [3] R 1 and the above R 2 Both of the above and R 3 and the above R 4 and (b) are optionally substituted monovalent aromatic hydrocarbon groups. [4] The composition according to any one of [1] to [3], further comprising a polymerization initiator, wherein the polymerization initiator includes a thermal base generator. [5] The composition according to any one of [1] to [4], further comprising a polymerization inhibitor. [6] The composition according to any one of [1] to [5], wherein the compound having at least one thiirane group or thietane group includes a compound represented by formula (II): [ka] [In formula (II), L 1x represents a single bond or a divalent group, and two L 1x may be the same or different. A 1x represents an oxygen atom or a sulfur atom, and two A 1x may be the same or different. However, if there are two A 1x At least one of the groups is a sulfur atom. mx represents 0 or 1, and two mx may be the same or different. nx represents an integer of 0 to 6. R 1x represents a monovalent substituent, and R 1x If there are multiple R 1x may be the same or different. R 2x represents a hydrogen atom or a monovalent substituent, and two R 2x may be the same or different.] [7] A molded article obtained by curing the composition according to any one of [1] to [6]. [8] A cured product of the composition according to any one of [1] to [6]. [9] A display device comprising the cured product according to [8].

[10] A solid-state imaging device comprising the cured product according to [8]. [Effects of the Invention]

[0007] According to the present invention, there is provided a composition containing a compound having at least one thiirane group or thietane group, which is capable of giving a cured product having excellent yellowing resistance. Some forms of the composition also have excellent film-forming properties. Furthermore, according to the present invention, there are provided a molded article obtained by curing such a composition, a cured product of such a composition, a display device including the cured product, and a solid-state imaging device including the cured product. DETAILED DESCRIPTION OF THE INVENTION

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

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

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

[0011] In this specification, unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more within the range that meets the conditions. When multiple substances corresponding to each component are present, the content of each component means the total amount of the multiple substances unless otherwise specified.

[0012] <Composition> The composition of one embodiment contains a compound represented by formula (I-1) or formula (I-2) (hereinafter sometimes referred to as "component (A)") and a compound having at least one thiirane group or thietane group (hereinafter sometimes referred to as "component (B)"). The composition of this embodiment makes it possible to provide a cured product that exhibits a high refractive index and excellent yellowing resistance. The composition of this embodiment may further contain a polymerization initiator (hereinafter sometimes referred to as "component (C)"), a polymerization regulator (hereinafter sometimes referred to as "component (D)"), etc.

[0013] Component (A): a compound represented by formula (I-1) or (I-2) The composition of this embodiment contains component (A). By including component (A) in the composition, the yellowing resistance of the resulting cured product can be improved. Although the reason for this effect is not entirely clear, it is thought that component (A) contributes to capturing components that contribute to coloring that may occur when component (B), described below, is heated.

[0014] [ka]

[0015] In formula (I-1), R 1 and R 2 each independently represents a monovalent substituent.

[0016] R 1 and R 2 Examples of the monovalent substituent represented by the formula (I) include monovalent hydrocarbon groups such as monovalent aliphatic chain hydrocarbon groups which may have a substituent, monovalent alicyclic hydrocarbon groups which may have a substituent, monovalent aromatic hydrocarbon groups which may have a substituent, and monovalent groups formed by a combination thereof (for example, aralkyl groups); hydroxy 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. Examples of the heterocyclic groups include an amino group, an aliphatic heterocyclic group having 4 to 20 carbon atoms, such as a pyrrolidinyl group, a pyrrolinyl group, an imidazolidinyl group, an imidazolinyl group, an oxazolinyl group, a thiazolyl group, a piperidinyl group, a morpholinyl group, a piperazinyl group, an indolyl group, an isoindolyl group, a quinolyl group, a thienyl group, a pyrrolyl group, and a furyl group, and an aromatic heterocyclic group having 3 to 20 carbon atoms; a halogen atom; a nitro group; a cyano group; a carboxy group; a sulfo group; a thiol group; a formyl group; a -SF3 group; and a -SF5 group. 1 and R 2 may be bonded to each other to form a ring together with the atoms to which they are bonded.

[0017] The methylene group (-CH2-) contained in the monovalent substituent is -O-, -S-, -NR1B -(R 1B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) It may be substituted with -CO-, -SO2-. Examples of groups in which a methylene group (-CH2-) contained in a monovalent substituent is substituted with -O- include alkoxy groups having 1 to 12 carbon atoms such as a methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, and octyloxy group; and alkoxyalkyl groups such as a methoxymethyl group, ethoxymethyl group, and methoxyethyl group.

[0018] Examples of monovalent aliphatic chain hydrocarbon groups include saturated or unsaturated aliphatic chain 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. The monovalent aliphatic chain hydrocarbon group may be linear or branched. The monovalent aliphatic chain hydrocarbon group typically has 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.

[0019] Examples of the substituent that the monovalent aliphatic chain hydrocarbon group may have include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxy group; an amino group; an acetyl group; a cyano group; and acidic groups such as a carboxy group, a sulfo group, and a carboxy group.

[0020] Examples of monovalent alicyclic hydrocarbon groups include saturated or unsaturated alicyclic hydrocarbon groups. More specifically, examples include monocyclic alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl; and polycyclic alicyclic hydrocarbon groups such as bicyclo[1.1.0]butyl, tricyclo[2.2.1.0]heptyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, adamantyl, bicyclo[4.3.2]undecyl, and tricyclo[5.3.1.1]dodecyl. The number of carbon atoms in the monovalent alicyclic hydrocarbon group is usually 3 to 20, preferably 3 to 10, more preferably 3 to 6, and even more preferably 5 or 6.

[0021] Examples of the substituent that the monovalent alicyclic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; hydroxy groups; amino groups; acetyl groups; cyano groups; and acidic groups such as carboxy, sulfo, and carboxy groups.

[0022] The monovalent aromatic hydrocarbon group may be monocyclic or polycyclic. Examples of the monovalent aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, and a fluorenyl group. The monovalent aromatic hydrocarbon group typically has 6 to 20 carbon atoms, and preferably has 6 to 10 carbon atoms.

[0023] Examples of the substituent that the monovalent aromatic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxy groups; amino groups; acetyl groups; cyano groups; and acidic groups such as carboxy, sulfo, and carboxy groups.

[0024] In the compound represented by formula (I-1), R 1 and R 2 From the viewpoint of yellowing resistance, preferably, at least one of them is a monovalent aromatic hydrocarbon group which may have a substituent, and more preferably, both of them are monovalent aromatic hydrocarbon groups which may have a substituent.

[0025] [ka]

[0026] In formula (I-2), R 3 and R 4 each independently represents a monovalent substituent. L 1 represents a divalent group.

[0027] R 3 and R 4 The monovalent substituent represented by R 1 and R 2 Examples of the monovalent substituent include those similar to those represented by the following formula:

[0028] In the compound represented by formula (I-2), R 3 and R 4 From the viewpoint of yellowing resistance, preferably, at least one of them is a monovalent aromatic hydrocarbon group which may have a substituent, and more preferably, both of them are monovalent aromatic hydrocarbon groups which may have a substituent.

[0029] L 1 Examples of the divalent group represented by the formula (1) include divalent hydrocarbon groups such as an optionally substituted divalent aliphatic chain hydrocarbon group; an optionally substituted divalent alicyclic hydrocarbon group; an optionally substituted divalent aromatic hydrocarbon group; and a divalent group formed by a combination thereof (e.g., an aralkylene group). The methylene group (-CH2-) contained in the divalent group can be -O-, -S-, -NR A -(R Arepresents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) may be substituted with -CO- or -SO2-.

[0030] Examples of divalent aliphatic chain hydrocarbon groups include saturated or unsaturated aliphatic chain hydrocarbon groups. More specifically, examples include alkanediyl groups such as methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl, undecanediyl, dodecanediyl, tridecanediyl, tetradecanediyl, pentadecanediyl, hexadecanediyl, heptadecanediyl, octadecanediyl, nonadecanediyl, and eicosanediyl. The divalent aliphatic chain hydrocarbon group may be linear or branched. The divalent aliphatic chain hydrocarbon group typically has 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.

[0031] Examples of the substituent that the divalent aliphatic chain hydrocarbon group may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; hydroxy group; amino group; acetyl group; and cyano group.

[0032] Examples of divalent alicyclic hydrocarbon groups include saturated or unsaturated alicyclic hydrocarbon groups. More specifically, examples include monocyclic alicyclic hydrocarbon groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cyclooctanediyl, cyclononanediyl, and cyclodecanediyl; and polycyclic alicyclic hydrocarbon groups such as bicyclo[1.1.0]butanediyl, tricyclo[2.2.1.0]heptanediyl, bicyclo[3.2.1]octanediyl, bicyclo[2.2.2]octanediyl, adamantanediyl, bicyclo[4.3.2]undecanediyl, and tricyclo[5.3.1.1]dodecanediyl. The number of carbon atoms in the divalent alicyclic hydrocarbon group is usually 3 to 20, preferably 3 to 10, more preferably 3 to 6, and even more preferably 5 or 6.

[0033] Examples of the substituent that the divalent alicyclic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; hydroxy groups; amino groups; acetyl groups; and cyano groups.

[0034] The divalent aromatic hydrocarbon group may be monocyclic or polycyclic. Examples of the divalent aromatic hydrocarbon group include a phenylene group, a naphthylene group, an anthracenediyl group, and a fluorenediyl group. The divalent aromatic hydrocarbon group usually has 6 to 20 carbon atoms, and preferably has 6 to 10 carbon atoms.

[0035] Examples of the substituent that the divalent aromatic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxy groups; amino groups; acetyl groups; and cyano groups.

[0036] In the compound represented by formula (I-2), L 1 is preferably an alkanediyl group. In this case, the alkanediyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.

[0037] Specific examples of component (A) are shown below, but are not limited to these.

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] From the viewpoint of availability, the molecular weight of component (A) is preferably 2000 or less, more preferably 1000 or less, and even more preferably 600 or less. From the viewpoint of volatility, the molecular weight of component (A) is preferably 100 or more, and more preferably 150 or more.

[0045] As the component (A), a commercially available product can be used as is.

[0046] The content of component (A) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, relative to 100 parts by mass of the total amount of component (B) described below, because this makes it easier to fully obtain the effects of the present invention, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less.

[0047] Component (B): a compound having at least one thiirane group or thietane group The composition of this embodiment contains component (B). Component (B) can be a curable compound. When the composition contains component (B), component (B) itself can be polymerized to give a cured product exhibiting a high refractive index. Compositions containing component (B) also tend to have excellent curability.

[0048] Component (B) can be any compound having at least one thiirane group or thietane group without any particular limitation. Component (B) may be, for example, a compound having at least one group represented by formula (II-a), and is preferably a compound having at least one group represented by formula (II-b).

[0049] [ka]

[0050] In formula (II-a), mx represents 0 or 1. R 2x represents a hydrogen atom or a monovalent substituent. * indicates the bond position.

[0051] [ka]

[0052] In formula (II-b), L 1x represents a single bond or a divalent group. mx represents 0 or 1. R 2x represents a hydrogen atom or a monovalent substituent. * indicates the bond position.

[0053] L 1x As the divalent group represented by 1 Examples of the divalent group include those similar to those represented by the following formula:

[0054] R 2x The monovalent substituent represented by R 1 and R 2 Examples of the monovalent substituent include those similar to those represented by the following formula:

[0055] mx represents 0 or 1. When mx is 0, it represents a three-membered ring structure which is a thiirane group, and when mx is 1, it represents a four-membered ring structure which is a thietane group. mx is preferably 0.

[0056] From the viewpoint of achieving a high refractive index of the cured product, component (B) is preferably a compound containing an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring; 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.

[0057] From the viewpoint of achieving a high refractive index of the cured product, the component (B) is preferably a compound represented by formula (II).

[0058] [ka]

[0059] In formula (II), L 1x represents a single bond or a divalent group, and two L 1x may be the same or different. A 1xrepresents an oxygen atom or a sulfur atom, and two A 1x may be the same or different. However, if there are two A 1x At least one of the groups is a sulfur atom. mx represents 0 or 1, and two mx may be the same or different. nx represents an integer of 0 to 6. R 1x represents a monovalent substituent, and R 1x If there are multiple R 1x may be the same or different. R 2x represents a hydrogen atom or a monovalent substituent, and two R 2x may be the same or different.

[0060] In the compound represented by formula (II), the two groups represented by formula (II-c) may be bonded to any of the 1- to 8-positions of the naphthalene ring. The groups represented by formula (II-c) on the naphthalene ring may be bonded, for example, to any two of the 1- to 4-positions (5- to 8-positions), or to any one of the 1- to 4-positions (5- to 8-positions) and any one of the 5- to 8-positions (1- to 4-positions). The groups represented by formula (II-c) on the naphthalene ring are preferably bonded to any one of the 1- to 4-positions (5- to 8-positions) and any one of the 5- to 8-positions (1- to 4-positions).

[0061] [ka]

[0062] In formula (X), L 1x , A 1x , mx, and R 2x has the same meaning as above, and * indicates the bonding position.

[0063] The compound of formula (II) is 1x When the group has a monovalent substituent represented by 1xmay be bonded to any of the 1- to 8-positions of the naphthalene ring, excluding the bonding position of the group represented by formula (II-c).

[0064] L 1x represents a single bond or a divalent group, and two L 1x In the compound represented by formula (II), the two L 1x Preferably, at least one of them is an alkanediyl group, and more preferably, both of them 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.

[0065] A 1x represents an oxygen atom or a sulfur atom, and two A 1x may be the same or different. However, if there are two A 1x In the compound represented by formula (II), at least one of the two A 1x Preferably, both of A and A are sulfur atoms. 1x As the number of sulfur atoms as the copolymer increases, a cured product exhibiting a higher refractive index can be obtained, and the curability tends to be better.

[0066] mx represents 0 or 1, and two mx may be the same or different, or may be the same. In the compound represented by formula (II), both of the two mx are preferably 0.

[0067] nx represents an integer of 0 to 6. nx is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 0.

[0068] R 1x represents a monovalent substituent, and R 1x If there are multiple R 1x may be the same or different, or may be the same.1x The monovalent substituent represented by R 2x Examples of the monovalent substituent include those similar to those represented by the following formula:

[0069] R 2x represents a hydrogen atom or a monovalent substituent, and two R 2x In the compound represented by formula (II), the two R 2x is preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group, more preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group having 1 to 6 carbon atoms, 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.

[0070] Examples of component (B) (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 formula (II-A), formula (II-B), formula (II-C), formula (II-D), formula (II-E), and formula (II-F) 1x , A 1x , mx, nx, R 1x , and R 2x has the same meaning as above.

[0071] [ka]

[0072] In formula (II-A), formula (II-B), formula (II-C), formula (II-D), formula (II-E), and formula (II-F), two L 1x Preferably, at least one of them is an alkanediyl group, and more preferably, both of them 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.

[0073] In Formula (II-A), Formula (II-B), Formula (II-C), Formula (II-D), Formula (II-E), and Formula (II-F), each of two mx is independently 0 or 1, and preferably 0. In Formula (II-A), Formula (II-B), Formula (II-C), Formula (II-D), Formula (II-E), and Formula (II-F), each of two mx is preferably 0.

[0074] In formula (II-A), formula (II-B), formula (II-C), formula (II-D), formula (II-E), and formula (II-F), nx each independently represents an integer of 0 to 6, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and particularly preferably 0.

[0075] In formula (II-A), formula (II-B), formula (II-C), formula (II-D), formula (II-E), and formula (II-F), two A 1x are each independently an oxygen atom or a sulfur atom. 1x At least one of A is a sulfur atom. 1x Preferably, both of are sulfur atoms.

[0076] In formula (II-A), formula (II-B), formula (II-C), formula (II-D), formula (II-E), and formula (II-F), two R 2x are each 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 are preferably identical.

[0077] Specific examples of component (B) (compound represented by formula (II)) are shown below, but the invention is not limited to these.

[0078] [ka]

[0079]

change

[0080]

change

[0081]

change

[0082]

change

[0083]

change

[0084]

change

[0085]

change

[0086]

change

[0087]

change

[0088]

change

[0089] [ka]

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] From the viewpoint of synthesis, the molecular weight of component (B) is preferably 2000 or less, more preferably 1000 or less, and even more preferably 750 or less. From the viewpoint of volatility, the molecular weight of component (B) is preferably 50 or more, more preferably 100 or more, and even more preferably 150 or more.

[0095] The compound represented by formula (II) as component (B) can be obtained by synthesizing a compound represented by formula (II-1) and reacting the compound represented by formula (II-1) with a sulfiding agent.

[0096] [ka]

[0097] In formula (II-1), L 1x , mx, nx, R 1x , and R 2x represents the same meaning as in the formula (I) above.

[0098] The compound represented by formula (II-1) can be obtained, for example, by a method including a step of reacting a compound represented by formula (II-1a) with a compound represented by formula (II-1b).

[0099] [ka]

[0100] In formula (II-1a), nx and R 1x represents the same meaning as above.

[0101] [ka]

[0102] In formula (II-1b), L 1x , mx, and R 2x has the same meaning as above, and X 1X represents a leaving group.

[0103] The reaction of the compound represented by formula (II-1a) with the compound represented by formula (II-1b) can be carried out, for example, in the presence of a base. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium hydride, lithium aluminum hydride, sodium borohydride, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, and cesium hydrogen carbonate; 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 the base used may be, for example, 0.0001 to 10 mol, preferably 0.001 to 5 mol, more preferably 0.01 to 4 mol, and even more preferably 0.1 to 3 mol, relative to 1 mol of the compound represented by Formula (II-1a).

[0104] Two or more types of bases may be used in combination. When used in combination, 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 is preferably used in combination with 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 more preferably a combination of a bicarbonate and a metal hydroxide. When used in combination, the two types may be added simultaneously or stepwise.

[0105] In the compound represented by formula (II-1b), X 1X Examples of the leaving group represented by formula (II-1b) include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, trifluoromethylsulfonyl group, perfluoroethylsulfonyl group, perfluoropropylsulfonyl group, and perfluorobutylsulfonyl group; and arylsulfonyl groups such as phenylsulfonyl group, p-toluenesulfonyl group, p-fluorophenylsulfonyl group, and pentafluorophenylsulfonyl group. Specific examples of the compound represented by formula (II-1b) include epihalohydrin compounds (L 1x is a methylene group, mx is 0, and R 2x is a hydrogen atom and X is a halogen atom). The amount of the compound represented by formula (II-1b) used may be, for example, 0.01 to 20 mol, and preferably 0.5 to 15 mol, relative to 1 mol 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).

[0106] The reaction of the compound represented by formula (II-1a) with the compound represented by formula (II-1b) is preferably carried out in a solvent. Examples of the solvent include water, as well as organic solvents such as ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, alcohols, glymes, esters, aliphatic nitriles, sulfoxides, and amides. Examples of the organic solvent include the following solvents:

[0107] 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. Halogenated aliphatic 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.

[0108] The temperature for the reaction of the compound represented by formula (II-1a) with 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.

[0109] 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 may be used as it is without isolation.

[0110] The compound represented by formula (II) can be obtained, for example, by a method including a step of reacting a compound represented by formula (II-1) with a sulfurizing agent.

[0111] 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 to form a thiirane ring (episulfide ring) or a thietane ring. Examples of sulfurizing agents include thiourea, methylthiourea, dimethylthiourea, trimethylthiourea, tetramethylthiourea, tetraethylthiourea, ethylenethiourea, phenylthiourea, diphenylthiourea, tolylthiourea, ditolylthiourea, sodium thiocyanate, and potassium thiocyanate. The amount of the sulfurizing agent used can be adjusted as needed depending on the oxygen atom to be substituted. The amount of the sulfurizing agent used is, for example, 0.01 to 20 mol, preferably 0.5 to 10 mol, per 1 mol of the compound represented by formula (II-1). Furthermore, by adjusting the amount of sulfurizing agent used, the reaction temperature, the reaction time, and the like, it is possible to replace both oxygen atoms in the compound represented by formula (II-1) with sulfur atoms, or to replace one oxygen atom in the compound represented by formula (II-1) with a sulfur atom.

[0112] The reaction between the compound represented by formula (II-1) and the sulfating agent is preferably carried out in a solvent. Examples of the solvent include the same solvents as those exemplified for 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 sulfating agent may be carried out at a temperature of, 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.

[0113] A polymerization inhibitor may be added to the reaction system to inhibit the polymerization of the compound represented by formula (II). Examples of the polymerization inhibitor 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, oleum, sulfuryl chloride, boric acid, arsenic acid, arsenous acid, pyroarsenic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphorus oxychloride, phosphorus oxybromide, phosphorus sulfide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, hydrocyanic acid, chromic acid, nitric anhydride, sulfuric anhydride, boron oxide, arsenic pentoxide, phosphorus pentoxide, chromic anhydride, 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, and cesium dihydrogen phosphate; 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, maleic acid, benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, salicylic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, benzoylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, benzilic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and trifluoroacetic anhydride; phosphoric acids such as mono-, di-, and trimethyl phosphate, mono-, di-, and triethyl phosphate, mono-, di-, and triisobutyl phosphate, mono-, di-, and tributyl phosphate, and mono-, di-, and trilauryl phosphate, and phosphorous acids in which the phosphate moiety thereof becomes a phosphite; Organophosphorus compounds such as dialkyldithiophosphates, typified 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, methyl hydroxyphenylacetate, ethyl hydroxyphenylacetate, 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, and 2,4,6-trichlorophenol; 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, metanilic acid, sulfanilic acid, 4B-acid, diaminostilbenesulfonic acid, biphenylsulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, peric acid, Laurent acid, and phenyl J acid Examples include:

[0114] The amount of the polymerization inhibitor used may be, for example, 0.0001 to 1.0 mol, preferably 0.001 to 0.5 mol, more preferably 0.01 to 0.25 mol, and even more preferably 0.05 to 0.15 mol, relative to 1 mol of the compound represented by formula (II). Among these, the polymerization inhibitor is preferably acetic acid, acetic anhydride, maleic acid, maleic anhydride, phosphoric acid, an alkali metal hydrogen phosphate, or an alkali metal dihydrogen phosphate.

[0115] The reaction product solution can be washed with an acidic aqueous solution to improve the stability over time of the compound represented by formula (II). Specific examples of acids used in the acidic aqueous solution include the acids exemplified above as polymerization inhibitors. The acids may be used alone or in combination of two or more. While the acidic aqueous solution generally tends to be effective at a pH of 6 or less, a more effective range is a pH of 3 or less. The acid used in the acidic aqueous solution is preferably an aqueous solution of hydrogen chloride (hydrochloric acid), sulfuric acid, phosphoric acid, and / or maleic acid.

[0116] Furthermore, a hydrogen sulfide adsorbent 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 (a zinc oxide-based adsorbent, manufactured by Kureha Oil & Fat Industries Co., Ltd.), Nionon 202A (an iron oxide-based adsorbent, manufactured by Ibuki Masashi Co., Ltd.), and Limonic (an iron hydroxide-based adsorbent, manufactured by Nippon Limonite Co., Ltd.). The hydrogen sulfide adsorbent can be added during the reaction or can be added and used in purification after the reaction.

[0117] The content of component (B) may be, for example, 30 to 99% by mass, based on the total amount of solids in the composition, since this makes it easier to fully obtain the effects of the present invention. The content of component (B) is, based on the total amount of the composition, preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, and is preferably 98% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.

[0118] The total amount of solids in the composition means the total amount of components contained in the composition excluding the solvent. The content of each component in the solids of the composition can be measured by known analytical means such as liquid chromatography or gas chromatography. The content of each component in the solids of the composition may be calculated from the formulation when the composition is prepared.

[0119] Component (C): Polymerization initiator The composition of this embodiment may further contain a component (C). The component (C) is not particularly limited as long as it can initiate polymerization of the component (B), but preferably contains a compound that generates an acid or a base upon heating and promotes cationic or anionic polymerization of the component (B). That is, the component (C) preferably contains a thermal acid generator or a thermal base generator, and more preferably contains a thermal base generator. A thermal acid generator is also called a thermal cationic polymerization initiator. A thermal base generator is also called a thermal anionic polymerization initiator.

[0120] A thermal acid generator is a compound capable of releasing a substance that initiates cationic polymerization by heat. Examples of thermal acid generators include aromatic diazonium salts, aromatic sulfonium salts, aliphatic sulfonium salts, aromatic iodonium salts, pyridinium salts, and cyclopentadienyl iron (II) complexes. When the photoacid generator is an onium salt, examples of the counter anion include hexafluoroantimonate, hexafluorophosphonate, tetrafluoroborate, and tetrakis(pentafluorophenyl)borate.

[0121] A thermal base generator is a compound capable of releasing a substance that initiates anionic polymerization by heat. Examples of the thermal base generator include ammonium salts, DBU (diazabicycloundecenium) salts, DBN (diazabicyclononenium) salts, biguanidium salts, aromatic dimethylurea, aliphatic dimethylurea, guanidinium salts, phosphazene salts, and imidazole salts.

[0122] The content of component (C) is preferably at least 0.1 parts by mass, more preferably at least 0.5 parts by mass, relative to 100 parts by mass of the total amount of component (B), from the viewpoint of improving curability and / or yellowing resistance, and is preferably at most 10 parts by mass, more preferably at most 8 parts by mass, from the viewpoint of improving the physical properties such as the mechanical properties of the cured product.

[0123] Component (D): Polymerization inhibitor The composition may further contain a component (D). Whether or not to contain a polymerization inhibitor in the composition is preferably determined, for example, taking into consideration the type of component (B). The component (D) is preferably dissolved or dispersed in a solvent. The component (D) contained in the composition may be added during the preparation of the composition or may be added after the production of component (B). By containing the component (D) in the composition, unintended polymerization of component (B) is suppressed, thereby improving the storage stability of the composition.

[0124] Examples of component (D) include the same polymerization inhibitors that are added to the reaction system to inhibit the polymerization of the compound represented by formula (II) that has been produced. Component (D) is preferably an organic carboxylic acid, more preferably an organic carboxylic acid having 10 or less carbon atoms, and even more preferably formic acid or acetic acid.

[0125] When the composition contains component (D), from the viewpoint of improving the storage stability of the composition, the content of component (D) is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, even more preferably 0.5 part by mass or more, and particularly preferably 1 part by mass or more, relative to 100 parts by mass of the total amount of component (B); and is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 25 parts by mass or less, and particularly preferably 10 parts by mass or less.

[0126] Examples of other components contained in the composition include resins, curable compounds other than component (B), solvents, additives, etc. Examples of additives include inorganic particles, fillers, polymerization initiator aids, sensitizers, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, UV absorbers, antioxidants, dispersants, etc.

[0127] (resin) The composition may contain one or more resins. By containing a resin in the composition, it is possible to impart developability to a cured product of the composition, and to adjust the mechanical properties and / or optical properties of the cured product and a molded product containing the cured product. Examples of resins include thermoplastic resins and curable resins. The curable resin may be a photocurable resin that is cured by irradiation with active energy rays, or a thermosetting resin that is cured by heat.

[0128] Examples of thermoplastic resins include olefin-based resins such as polyethylene resin, polypropylene resin, and polycycloolefin resin; (meth)acrylic resins such as poly(meth)acrylate resin; styrene-based resins such as polystyrene-based resin, styrene-acrylonitrile-based resin, and acrylonitrile-butadiene-styrene-based resin; vinyl-based resins such as polyvinyl chloride-based resin, polyvinylidene chloride-based resin, polyvinyl acetate-based resin, polyvinyl butyral-based resin, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol-based resin; polyester-based 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.

[0129] Examples of the curable resin include resins having a photopolymerizable group or a thermally polymerizable group, such as (meth)acrylic resins, epoxy resins, melamine resins, unsaturated polyester resins, phenolic resins, urea resins, alkyd resins, and polyimide resins.

[0130] Other examples of resins include alkali-soluble resins. By including an alkali-soluble resin in the composition, it is possible to impart developability to a cured product of the composition. The alkali-soluble resin means a resin that is soluble in an aqueous alkaline solution. Specific examples include resins having a carboxy group and / or a phenolic hydroxyl group.

[0131] From the viewpoint of improving the developability and solvent resistance of a cured product of the composition, the acid value of the alkali-soluble resin is preferably 10 to 170 mgKOH / g, more preferably 20 to 150 mgKOH / g, and even more preferably 30 to 140 mgKOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the alkali-soluble resin, and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

[0132] Another example of the resin is a high refractive index resin, which means a resin having a refractive index of 1.60 or more at a wavelength of 550 nm.

[0133] The weight average molecular weight (Mw) of the resin, measured by gel permeation chromatography (GPC) in terms of standard polystyrene, may be, for example, 5 million to 2 million, preferably 1,000 to 1 million, and more preferably 1,500 to 750,000. The Mw of the resin can be adjusted by appropriately combining reaction conditions such as the selection of raw materials used, the charging method, the reaction temperature, and the reaction time.

[0134] When the composition contains a resin, the resin content is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, based on the total amount of solids in the composition.

[0135] (Curable compounds other than component (B)) The composition may contain one or more curable compounds other than component (B). By including a curable compound other than component (B), the viscosity or curability of the composition can be adjusted, and the mechanical and / or optical properties of the resulting cured product and molded products containing the same can be adjusted.

[0136] Examples of curable compounds other than component (B) include epoxy compounds other than component (B), oxetane compounds other than component (B), hydroxy compounds, vinyl ether compounds, allyl compounds, thiol compounds, polyphenol compounds, iso(thio)cyanate compounds, and acid anhydrides.

[0137] When the composition contains a curable compound other than the component (B), the content of the curable compound other than the component (B) is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total amount of solids in the composition, and is preferably 30% by mass or less, more preferably 20% by mass or less.

[0138] (solvent) The composition may contain one or more solvents. The solvent is preferably one that can dissolve or disperse component (B), and more preferably one that can also dissolve or disperse components other than component (B). Examples of the solvent include the solvents exemplified in the reaction between the compound represented by formula (Ia) and the compound represented by formula (Ib) (organic solvents), ester solvents (solvents that contain -COO- in the molecule but do not contain -O-), ether solvents (solvents that contain -O- in the molecule but do not contain -COO-), ether ester solvents (solvents that contain -COO- and -O- in the molecule), ketone solvents (solvents that contain -CO- in the molecule but do not contain -COO-), alcohol solvents (solvents that contain OH in the molecule but do not contain -O-, -CO-, or -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

[0139] 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.

[0140] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methylanisole.

[0141] 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-methyl ...propionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl 2-ethoxypropionate, methyl Examples of the alkyl ether acetate include ethyl 2-methoxypropionate, 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.

[0142] 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.

[0143] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0144] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0145] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0146] When the composition contains a solvent, the content of the solvent is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, and preferably 1000 parts by mass or less, more preferably 500 parts by mass or less, relative to 100 parts by mass of the total solid content of the composition. When the composition contains a solvent, the solid content concentration of the composition is preferably 5 to 60% by mass, more preferably 10 to 50% by mass.

[0147] <Cured products and molded products> A cured product in one embodiment is a cured product of the composition. A molded product in one embodiment is obtained by curing the composition and includes a cured product of the composition. Because the composition has excellent film-forming properties, curing properties, etc., it can be suitably used as a curable material for producing a cured product or a molded product containing the same. The cured product can be obtained by curing component (B) and the like in the composition by at least one of irradiation with active energy rays and heat, preferably heat. The shape of the molded product containing the cured product is not particularly limited and may include a film (membrane), plate, lens, powder, granules, non-spherical particles, crushed particles, porous, continuous aggregate, fiber, tube, hollow fiber, etc., and may be any shape depending on the intended use of the molded product.

[0148] The method for obtaining a molded product from the composition is not particularly limited, and examples thereof include a method in which a film is formed on a substrate and then shaped by etching or the like, an injection molding method, and a cast polymerization molding method.

[0149] In the cast polymerization molding method, for example, the composition is poured into a mold, degassed as necessary, and then cured by heating in an oven or the like, and the resulting molded product is removed. The molded product thus removed can also be irradiated with active energy rays for additional curing.

[0150] When forming a film as a molded product on a substrate, the composition is applied to the substrate, and if necessary, dried to form a coating film (coating layer), and the coating film (coating layer) is cured to obtain a molded product that is a cured film (cured layer). The molded product may be a patterned cured film (cured layer). A patterned cured film can be obtained by patterning using a method such as photolithography, inkjet printing, or printing. The patterning method may be, for example, a photolithography method. The photolithography method is a method in which a composition is applied to a substrate, and if necessary, dried to form a coating film (coating layer), and the coating film (coating layer) is exposed to light through a photomask, and the exposed coating film (coating layer) is developed.

[0151] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, silica-coated soda lime glass, and alkali-free glass; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; and substrates having aluminum, silver, or silver / copper / palladium alloy thin films formed thereon. Methods for applying the composition to the substrate include spin coating, slit coating, and slit and spin coating.

[0152] The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, from light with wavelengths in this range, light with wavelengths 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, and halogen lamps.

[0153] After the pattern exposure, the exposed coating film (coating layer) may be heated before development (pre-development bake).

[0154] Examples of the developer used for development include aqueous solutions and solvents containing alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. Examples of the solvent include the solvents (organic solvents) exemplified in the reaction between the compound represented by formula (Ia) and the compound represented by formula (Ib) or the solvents described above. The developer may contain a surfactant. Examples of the development method include a puddle method, a dipping method, and a spray method. The patterned cured film (cured layer) obtained by development may be further heated (post-baked).

[0155] Because the cured product or a molded product containing the cured product is formed from the composition, it can exhibit a high refractive index, and the refractive index can be controlled to a desired value by adjusting the composition, etc. The refractive index of the cured product or a molded product containing the cured product at a wavelength of 550 nm may be 1.650 or more, 1.680 or more, 1.700 or more, 1.720 or more, 1.740 or more, 1.750 or more, or 1.760 or more. The refractive index of the cured product or a molded product containing the cured product at a wavelength of 550 nm may be, for example, 2.000 or less, or 1.900 or less.

[0156] The refractive index at a wavelength of 550 nm of a cured product or a molded product containing the same can be measured, for example, by the following method. First, a coating film is formed on a substrate, and the coating film is cured to obtain a substrate with a cured film formed thereon. Next, the transmission spectrum and reflection spectrum of the substrate with the cured film formed thereon are measured at wavelengths of 300 nm to 800 nm using a visible-ultraviolet spectrophotometer (e.g., JASCO Corporation's "V-650") equipped with an integrating sphere unit (e.g., JASCO Corporation's "ISV-922"). Next, the true reflection spectrum obtained by subtracting and smoothing the increase or decrease due to interference in the reflection spectrum from the transmission spectrum and reflection spectrum is used to calculate the refractive index at a wavelength of 550 nm of the cured product or a molded product containing the same based on the value at a wavelength of 550 nm and the refractive index of the substrate using Fresnel's formula (e.g., Hecht Optics I, Original Work, 5th Edition, Maruzen Publishing, 2018, pp. 209-226). This allows the refractive index at a wavelength of 550 nm of the cured product or a molded product containing the same to be determined.

[0157] <Usage> Applications of the cured or molded products include, for example, glass substitutes and surface coating materials; coating materials for window glass, lighting glass, and light source protection glass for homes, facilities, transportation equipment, etc.; window films for homes, facilities, transportation equipment, etc.; interior and exterior materials and interior and exterior paints for homes, facilities, transportation equipment, etc., and coating films formed by such paints; alkyd resin lacquer paints and coating films formed by such paints; acrylic lacquer paints and coating films formed by such paints; components for ultraviolet light sources such as fluorescent lamps and mercury lamps; materials for blocking electromagnetic waves generated by 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 films; anti-fading agents for printed materials, dyed materials, dyes and pigments, etc.; protective films for polymer supports (e.g., plastic parts for machinery and automotive parts); printing overcoats; inkjet media coatings; matte laminates; optical light films; safety glass / windshield interlayers; electrochromic / photochromic applications; overlaminate films; solar heat control films; cosmetics such as sunscreen creams, shampoos, conditioners, and hair styling products; textiles and fibers for clothing such as sportswear, stockings, and hats; household interior goods 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 and pickup lenses described below), mirrors, and photographic materials; stationery such as mold films, transfer stickers, anti-graffiti films, tapes, and inks; sign boards, markers, and the like, and surface coating materials for them; substrates used in optical devices, etc.; optical waveguides; holograms; LED encapsulants, etc.

[0158] The molded article is suitably used as a lens, which is an optical component used in optical devices. Examples of optical devices include solid-state imaging devices and display devices. In solid-state imaging devices, lenses are used to improve the efficiency of light collection onto each photoelectric conversion element. In display devices, lenses are used to improve the efficiency of light extraction from pixels. The lenses may be microlenses. Examples of display devices include liquid crystal display devices and organic EL display devices.

[0159] Conventionally, inorganic compounds such as zirconium oxide and titanium oxide have been known as high refractive index materials. However, when producing a molded product containing a high refractive index material made of an inorganic compound, molding can be difficult, for example, because etching is difficult to proceed. Furthermore, the high refractive index material can scatter during molding, causing contamination problems. These problems can be solved by using the high refractive index material of the present embodiment, which is an organic compound.

[0160] A cured product of the composition of this embodiment can be suitably used as a main chain scission-type positive resist. When forming a resist pattern using a cured product of the composition of this embodiment, irradiation with ionizing radiation or the like (e.g., electron beam, KrF laser, ArF laser, EUV laser, etc.) cleaves the main chains of the polymers (A) and (B) constituting the cured product in the irradiated areas of the resist film, resulting in a lower molecular weight. This creates a difference in solubility in a developer between the exposed and unexposed areas, resulting in the formation of a resist pattern. A resist pattern using a cured product of the composition of this embodiment can be used to form resist patterns in the manufacture of printed circuit boards such as build-up boards; semiconductors; photomasks; molds; and the like. [Example]

[0161] 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, "parts" means "parts by mass" unless otherwise specified.

[0162] [Synthesis Example 1] <Synthesis of Compound (B-1)> Synthesis of compound (B-1a) [ka]

[0163] A four-neck flask equipped with a Dimroth condenser and a thermometer was conditioned under a nitrogen atmosphere, and 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 a separate flask and completely dissolved, and then added dropwise to the four-neck 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 a compound represented by formula (B-1a) (compound (B-1a)).

[0164] 1 H-NMR analysis and LC-MS measurement confirmed that compound (B-1a) was produced. 1 H-NMR (deuterated chloroform) δ: 8.37-8.39 (1H), 7.85 (1H), 7.39-7.70 (4H), 3.08-3.29 (5H), 2.94-2.98 (1H), 2.57-2.81 (3H), 2.39-2.41 (1H) LC-MS: [M+H] + =305.5

[0165] Synthesis of compound (B-1) [ka]

[0166] A four-neck flask equipped with a Dimroth condenser and a thermometer was filled with nitrogen, and 3 parts of compound (B-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 a compound represented by formula (B-1) (compound (B-1)).

[0167] 1 H-NMR analysis and LC-MS measurement confirmed that compound (B-1) was produced. 1 H-NMR (deuterated chloroform) δ: 8.39-8.43 (1H), 7.86 (1H), 7.40-7.74 (4H), 3.40-3.53 (2H), 3.04-3.18 (2H), 2.78-2.96 (2H), 2.47-2.49 (1H), 2.35-2.36 (1H), 2.14-2.16 (1H), 1.93-1.94 (1H) LC-MS: [M+H] + =337.5

[0168] [Examples 1 to 5 and Comparative Examples 1 to 3] <Preparation of Composition> The components shown in Table 1 were placed in a flask in the amounts (unit: parts by mass) shown in Table 1 and stirred to prepare liquid compositions of Examples 1 to 5 and Comparative Examples 1 to 3. The compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were transparent when visually inspected, and it was confirmed that the components were uniformly dissolved.

[0169] The details of the abbreviations of the ingredients shown in Table 1 are as follows: Component (A): a compound represented by formula (I-1) or (I-2) (A-1): Compound (I-1-A) represented by the following formula (manufactured by Tokyo Chemical Industry Co., Ltd.) [ka] (A-2): Compound (I-1-B) represented by the following formula (manufactured by Sigma-Aldrich) [ka] (A-3): Compound (I-1-C) represented by the following formula (manufactured by Tokyo Chemical Industry Co., Ltd.) [ka] (A-4): Compound (I-2-A) represented by the following formula (manufactured by Tokyo Chemical Industry Co., Ltd.) [ka] (A-5): Compound (I-2-B) represented by the following formula (manufactured by Tokyo Chemical Industry Co., Ltd.) [ka] Component (a) (compounds other than component (A)) (a-1): Compound (aA) represented by the following formula (ADK STAB (registered trademark) 135A (manufactured by ADEKA Corporation)) [ka] (a-2): Compound (aB) represented by the following formula (Sumilizer (registered trademark) GP (manufactured by Sumitomo Chemical Co., Ltd.)) [ka] (a-3): Compound (aC) represented by the following formula (Irganox (registered trademark) 3114 (manufactured by BASF Japan Ltd.)) [ka] Component (C): Polymerization initiator (C-1): Thermal base generator (U-CAT 1102 (manufactured by San-Apro Co., Ltd.)) (E) Component: Solvent (E-1): PGMEA (propylene glycol monomethyl ether acetate)

[0170] <Evaluation test> (1) Formation of hardened film Approximately 3 mL of each of the compositions of Examples 1 to 5 and Comparative Examples 1 to 3 was dropped onto an alkali-free glass plate (0.7 mm thick, Corning Eagle XG) and spin-coated at 1000 rpm for 20 seconds using a spin coater (Mikasa MS-B100). The alkali-free glass plate on which the coating film was formed was heated at 60°C for 2 minutes to remove the solvent. The alkali-free glass plate on which the coating film was formed was then post-baked at 120°C for 10 minutes to obtain an alkali-free glass plate on which a cured film was formed. The thickness of the cured film on the alkali-free glass plate was measured using a stylus film thickness meter (Bruker DekTak XT), and the thickness was 1.5 μm in all cases.

[0171] (2) Refractive index The transmission and reflection spectra of the alkali-free glass on which the cured film was formed, as prepared in (1) above, were measured at wavelengths from 300 nm to 800 nm using a visible-ultraviolet spectrophotometer (JASCO Corporation, "V-650") equipped with an integrating sphere unit (JASCO Corporation, "ISV-922"). The true reflection spectra were obtained by subtracting and smoothing the interference-related fluctuations in the transmission and reflection spectra. The refractive index of the cured film at a wavelength of 550 nm was calculated using the value at a wavelength of 550 nm and the refractive index of an alkali-free glass plate (Corning Incorporated, "Eagle XG") according to Fresnel's formula (Hecht Optics I, 5th Edition, Maruzen Publishing, 2018, pp. 209-226). The results are shown in Table 1.

[0172] (3) Film formability For the compositions of Examples 1 to 5 and Comparative Examples 1 to 3, coating films were formed by the following method, and film-forming properties were evaluated. Approximately 3 mL of the composition was dropped onto an alkali-free glass plate (0.7 mm thick, Corning Eagle XG) and spin-coated at 1000 rpm for 20 seconds using a spin coater (Mikasa MS-B100) to form a coating film. The alkali-free glass plate on which the coating film had been formed was heated at 60°C for 2 minutes to remove the solvent.

[0173] The resulting coating film 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 hole defect refers to a state in which a hole of 1 mm or more in diameter appears in the coating film, exposing the alkali-free glass plate. A cissing defect refers to a state in which the exposed portion of the alkali-free glass plate is not observed, but the film thickness is partially thinned around environmental foreign matter, etc., resulting in crater-like defects of less than 1 mm in diameter. A result of 4 or 5 can be said to indicate good film-forming properties. 5: Neither pitting nor cissing defects were observed. 4: 2 or more but less than 5 cissing defects were observed. 3: 2 or more but less than 5 pit defects were observed. 2: Two or more but less than five hole defects and cissing defects were observed, and the coating film turned white. 1: Five or more holes and five or more cissing defects were observed, and the coating film was whitened.

[0174] (4) Yellowing resistance The alkali-free glass plate on which the cured film was formed, as prepared in (1) above, was used to evaluate the yellowing resistance of the composition (cured product) according to the following evaluation criteria. The alkali-free glass plate on which the cured film was formed was left standing for 5 minutes on a hot plate heated to 260°C, and 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) was calculated to evaluate the yellowing resistance. The results are shown in Table 1. A score of 4 or 5 indicates good yellowing resistance. 5: The change in transmittance was 0% or more and less than 5%. 4: The change in transmittance was 5% or more and less than 10%. 3: The change in transmittance was 10% or more and less than 12%. 2: The change in transmittance was 12% or more and less than 15%. 1: The change in transmittance was 15% or more.

[0175] [Table 1]

[0176] As shown in Table 1, the compositions of the examples were superior in yellowing resistance compared to the compositions of the comparative examples. The compositions of the examples were also superior in film-forming properties. These results confirmed that the compositions of the present invention, which contain a compound having at least one thiirane group or thietane group, can provide cured products with excellent yellowing resistance.

Claims

1. A composition comprising a compound represented by formula (I-1) or (I-2) and a compound having at least one thiirane group or thietane group. 【Chemical 1】 [In formula (I-1), R １ and R ２ each independently represents a monovalent substituent. 【Chemistry 2】 [In formula (I-2), R ３ and R ４ each independently represents a monovalent substituent. L １ represents a divalent group.

2. The R １ and the R ２ and at least one of the above R ３ and the R ４ The composition according to claim 1 , wherein at least one of the above is a monovalent aromatic hydrocarbon group which may have a substituent.

3. The R １ and the R ２ and both of the above R ３ and the R ４ and (b) are optionally substituted monovalent aromatic hydrocarbon groups.

4. The composition of claim 1 further comprising a polymerization initiator, the polymerization initiator comprising a thermal base generator.

5. The composition of claim 1 further comprising a polymerization inhibitor.

6. The composition according to claim 1 , wherein the compound having at least one thiirane group or thietane group comprises a compound represented by formula (II): 【Chemistry 3】 [In formula (II), L １ｘ represents a single bond or a divalent group, and two L １ｘ may be the same or different. A １ｘ represents an oxygen atom or a sulfur atom, and two A １ｘ may be the same or different. However, if there are two A １ｘ At least one of the groups is a sulfur atom. mx represents 0 or 1, and two mx may be the same or different. nx represents an integer of 0 to 6. R １ｘ represents a monovalent substituent, and R １ｘ If there are multiple R １ｘ may be the same or different. R ２ｘ represents a hydrogen atom or a monovalent substituent, and two R ２ｘ may be the same or different.

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

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

9. A display device comprising the cured product according to claim 8.

10. A solid-state imaging device comprising the cured product according to claim 8 .

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