Composition and cured product thereof, molding, display device and solid-state imaging element

Abstract

To provide a composition capable of providing a cured product exhibiting a high refractive index without impairing film forming properties.SOLUTION: There is provided a composition comprising (A) a compound having at least one of a thiirane group or a thietane group and (B) a compound represented by the formula (Z). [In the formula (Z), Ri represents a monovalent substituent and when there are plurality of Ris, the plurality of Ris may be the same or different. p represents any integer from 1 to 8. q represents any integer from 0 to 7. Provided that the sum of p and q is 8 or less.]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] In the field of optical instruments, there is a demand for high refractive index materials. By using high refractive index materials, lenses can be obtained, and the lenses can control the optical path in optical instruments. In solid-state imaging devices, lenses are used to improve the light collection efficiency of each photoelectric conversion element. In display devices, lenses are used to improve the light extraction efficiency from pixels. Conventionally, various high refractive index materials have been developed, and it is known that inorganic fillers are added to increase the refractive index. On the other hand, the addition of inorganic fillers can cause various problems, such as light scattering due to aggregation of inorganic fillers and contamination of the surroundings by metal ions during processing. As conventional high refractive index materials, for example, compositions containing specific (meth)acrylate compounds are known (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2011 / 102258 Summary of the Invention [Problem to be solved by the invention]

[0004] A main object of the present invention is to provide a composition that is capable of giving a cured product exhibiting a high refractive index without impairing film-forming properties. [Means for solving the problem]

[0005] The present invention provides a composition according to any one of [1] to [4], a molded product according to [5], a cured product according to [6], a display device according to [7], and a solid-state imaging device according to [8]. [1] A composition comprising (A) a compound having at least one thiirane group or thietane group, and (B) a compound represented by formula (Z): [ka] [In formula (Z), R i represents a monovalent substituent, R i If there are multiple, there are multiple R i may be the same or different. and p represents an integer of 1 to 8. q represents an integer of 0 to 7. However, the sum of p and q is equal to or less than 8.] [2] The composition according to [1], further comprising a polymerization initiator (C). [3] (D) The composition according to [1] or [2], further comprising a polymerization inhibitor. [4] The composition according to any one of [1] to [3], wherein (A) the compound having at least one thiirane group or thietane group is a compound represented by formula (I): [ka] [In formula (I), L represents a single bond or a divalent group, and the two L's may be the same or different. A 1 represents an oxygen atom or a sulfur atom, and there are two A 1 may be the same or different. However, if there are two A 1 At least one of the groups is a sulfur atom. m represents 0 or 1, and two m's may be the same or different. n represents an integer of 0 to 6. R 1 represents a monovalent substituent, R 1 If there are multiple, there are multiple R 1 may be the same or different. R 2 represents a hydrogen atom or a monovalent substituent, and two R2 may be the same or different.] [5] A molded product obtained by curing the composition according to any one of [1] to [4]. [6] A cured product of the composition according to any one of [1] to [4]. [7] A display device comprising the cured product according to [6]. [8] A solid-state imaging device comprising the cured product according to [6]. Effect of the Invention

[0006] According to the present invention, there is provided a composition capable of giving a cured product exhibiting a high refractive index without impairing film-forming properties. Also, according to the present invention, there are provided a molded product using 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 PREFERRED EMBODIMENTS

[0007] Hereinafter, embodiments of the present invention will be described in detail, however, the present invention is not limited to the following embodiments.

[0008] In this specification, a numerical range indicated using "~" indicates a range including the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper limit or lower limit value described in one numerical range may be replaced with the upper limit or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in this specification, the upper limit or lower limit value of the numerical range may be replaced with a value shown in the examples.

[0009] In this specification, (meth)acrylate means acrylate or the corresponding methacrylate, and the same applies to other similar expressions such as (meth)acryloyl group, (meth)acrylic acid ester, etc.

[0010] In this specification, unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more within the range of the conditions. When multiple substances corresponding to each component exist, the content of each component means the total amount of the multiple substances unless otherwise specified.

[0011] <Composition> The composition of one embodiment contains (A) a compound having at least one thiirane group or thietane group (hereinafter, sometimes referred to as a "sulfur-containing heterocyclic compound") and (B) a compound represented by formula (Z) (hereinafter, sometimes referred to as a "compound (Z)"). The composition of this embodiment makes it possible to give a cured product that exhibits a high refractive index without impairing film-forming properties. The composition of this embodiment may further contain (C) a polymerization initiator, (D) a polymerization inhibitor, etc.

[0012] (A) Component: Sulfur-containing heterocyclic compound The composition of the present embodiment contains component (A). Component (A) may be a curable compound. When the composition contains component (A), component (A) is polymerized to give a cured product exhibiting a high refractive index. The composition containing component (A) also has excellent film-forming properties.

[0013] The component (A) can be any compound having at least one thiirane group or thietane group without any particular limitation. The component (A) may be, for example, a compound having at least one group represented by formula (X0), and is preferably a compound having at least one group represented by formula (X1).

[0014] [ka]

[0015] In formula (X0), m represents 0 or 1. R 2 represents a hydrogen atom or a monovalent substituent. * indicates the bond position.

[0016] [ka]

[0017] In formula (X1), L represents a single bond or a divalent group. m represents 0 or 1. R 2 represents a hydrogen atom or a monovalent substituent. * indicates the bond position.

[0018] Examples of the divalent group represented by L 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 consisting of a combination thereof (e.g., an aralkylene group). The methylene group (-CH2-) contained in the divalent group can be -O-, -S-, -NR A -(R A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) may be substituted with -CO-, -SO2-, or -SO2-.

[0019] Examples of the divalent aliphatic chain hydrocarbon group include saturated or unsaturated aliphatic chain hydrocarbon groups. More specifically, examples include alkanediyl groups such as 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, and eicosanediyl group. The divalent aliphatic chain hydrocarbon group may be linear or branched. The number of carbon atoms in the divalent aliphatic chain hydrocarbon group is usually 1 to 20, preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.

[0020] Examples of the substituent that the divalent 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; and a cyano group.

[0021] Examples of the divalent alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups. More specifically, examples include monocyclic alicyclic hydrocarbon groups such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cyclooctanediyl group, cyclononanediyl group, and cyclodecanediyl group; and polycyclic alicyclic hydrocarbon groups such as bicyclo[1.1.0]butanediyl group, tricyclo[2.2.1.0]heptanediyl group, bicyclo[3.2.1]octanediyl group, bicyclo[2.2.2.]octanediyl group, adamantanediyl group, bicyclo[4.3.2]undecanediyl group, and tricyclo[5.3.1.1]dodecanediyl group. 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.

[0022] Examples of the substituent that the divalent alicyclic hydrocarbon group may have include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms), such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, or decyl group; a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a hydroxy group; an amino group; an acetyl group; and a cyano group.

[0023] 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 number of carbon atoms in the divalent aromatic hydrocarbon group is usually 6 to 20, and preferably 6 to 10.

[0024] 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.

[0025] R 2 Examples of the monovalent substituent represented by the formula (I) include monovalent hydrocarbon groups such as a monovalent aliphatic chain hydrocarbon group which may have a substituent, a monovalent alicyclic hydrocarbon group which may have a substituent, a monovalent aromatic hydrocarbon group which may have a substituent, and a monovalent group consisting of a combination thereof (for example, an aralkyl group); a hydroxy group; and one or two alkyl groups having 1 to 6 carbon atoms such as an amino group, a monomethylamino group, a monoethylamino group, a dimethylamino group, a diethylamino group, or a methylethylamino group. Examples of the heterocyclic groups include 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. The methylene group (-CH2-) contained in the monovalent substituent can be -O-, -S-, -NR B -(R B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) may be substituted with -CO-, -SO2-, or -O2-. Examples of the group 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, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group; and alkoxyalkyl groups, such as a methoxymethyl group, an ethoxymethyl group, and a methoxyethyl group.

[0026] Examples of the monovalent aliphatic chain hydrocarbon group include saturated or unsaturated aliphatic chain hydrocarbon groups. More specifically, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups can be mentioned. The monovalent aliphatic chain hydrocarbon group may be linear or branched. The number of carbon atoms in the monovalent aliphatic chain hydrocarbon group is usually 1 to 20, preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.

[0027] 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; and a cyano group.

[0028] Examples of the monovalent alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups. More specifically, examples include monocyclic alicyclic hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group; and polycyclic alicyclic hydrocarbon groups such as bicyclo[1.1.0]butyl group, tricyclo[2.2.1.0]heptyl group, bicyclo[3.2.1]octyl group, bicyclo[2.2.2.]octyl group, adamantyl group, bicyclo[4.3.2]undecyl group, and tricyclo[5.3.1.1]dodecyl group. 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.

[0029] 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 a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group; halogen atoms such as a fluorine atom, chlorine atom, bromine atom, and iodine atom; a hydroxy group; an amino group; an acetyl group; and a cyano group.

[0030] 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 number of carbon atoms in the monovalent aromatic hydrocarbon group is usually 6 to 20, and preferably 6 to 10.

[0031] 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 a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, or decyl group; halogen atoms such as a fluorine atom, chlorine atom, bromine atom, or iodine atom; a hydroxy group; an amino group; an acetyl group; and a cyano group.

[0032] m represents 0 or 1. When m is 0, it represents a three-membered ring structure which is a thiirane group, and when m is 1, it represents a four-membered ring structure which is a thietane group. m is preferably 0.

[0033] From the viewpoint of a high refractive index of the cured product, the component (A) 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, and more preferably a naphthalene ring.

[0034] From the viewpoint of achieving a high refractive index of the cured product, the component (A) is preferably a compound represented by formula (I).

[0035] [ka]

[0036] In formula (I), L represents a single bond or a divalent group, and the two L's may be the same or different. A 1 represents an oxygen atom or a sulfur atom, and there are two A 1 may be the same or different. However, if there are two A 1 At least one of the groups is a sulfur atom. m represents 0 or 1, and two m's may be the same or different. n represents an integer of 0 to 6. R 1 represents a monovalent substituent, R 1 If there are multiple, there are multiple R 1 may be the same or different. R 2 represents a hydrogen atom or a monovalent substituent, and two R 2 may be the same or different. L has the same meaning as above, m has the same meaning as above, R 2 has the same meaning as above.

[0037] In compound (I), the two groups represented by formula (X) may be bonded to any of the 1-8 positions of the naphthalene ring. The groups represented by formula (X) on the naphthalene ring may be bonded to any two of the 1-4 positions (5-8 positions), or to any one of the 1-4 positions (5-8 positions) and any one of the 5-8 positions (1-4 positions). The groups represented by formula (X) on the naphthalene ring are preferably bonded to any one of the 1-4 positions (5-8 positions) and any one of the 5-8 positions (1-4 positions).

[0038] [ka]

[0039] In formula (X), L, A 1 , m, and R 2 has the same meaning as above, and * indicates the bonding position.

[0040] Compound (I) has one or more R 1 When the aryl group has a monovalent substituent represented by 1 may be bonded to any one of the 1-8 positions of the naphthalene ring excluding the bonding position of the group represented by formula (X).

[0041] L represents a single bond or a divalent group, and the two L's may be the same or different, or may be the same. In compound (I), at least one of the two L's is preferably an alkanediyl group, and more preferably both are alkanediyl groups. In this case, the number of carbon atoms of the alkanediyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.

[0042] A 1 represents an oxygen atom or a sulfur atom, and there are two A 1 may be the same or different. However, if there are two A 1 At least one of the A's is a sulfur atom. 1 Preferably, both of A are sulfur atoms. 1 As the number of sulfur atoms as the copolymer increases, a cured product exhibiting a higher refractive index can be obtained, and the film-forming property tends to be more excellent.

[0043] m represents 0 or 1, and two m's may be the same or different, or may be the same. In compound (I), preferably, both of the two m's are 0.

[0044] n represents an integer of 0 to 6. n is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 0.

[0045] R 1 represents a monovalent substituent, R 1 If there are multiple, there are multiple R 1 may be the same or different, or may be the same. 1 The monovalent substituent represented by R 2 Examples of the monovalent substituent include those similar to those represented by the following formula:

[0046] R 2 represents a hydrogen atom or a monovalent substituent, and two R 2 may be the same or different, or may be the same. In compound (I), the two R 2 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.

[0047] Examples of the component (A) (compound (I)) include compounds represented by formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), and formula (If). 1 , m, n, R 1 , and R 2 has the same meaning as above.

[0048] [ka]

[0049] In the formulae (Ia), (Ib), (Ic), (Id), (Ie), and (If), preferably, at least one of the two L's is an alkanediyl group, 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.

[0050] In formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), and formula (If), each of the two m's is independently 0 or 1, and preferably 0. In formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), and formula (If), each of the two m's is preferably 0.

[0051] In formulas (Ia), (Ib), (Ic), (Id), (Ie), and (If), n is each independently 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.

[0052] In the formulas (Ia), (Ib), (Ic), (Id), (Ie), and (If), 1 are each independently an oxygen atom or a sulfur atom. 1 At least one of A is a sulfur atom. 1 Preferably, both are sulfur atoms.

[0053] In formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), and formula (If), two R 2 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. 2 are preferably identical.

[0054] Specific examples of the component (A) (compound (I)) are shown below, but the invention is not limited to these.

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] From the viewpoint of synthesis, the molecular weight of component (A) 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 (A) is preferably 50 or more, more preferably 100 or more, and even more preferably 150 or more.

[0072] Compound (I) as component (A) can be obtained by synthesizing a compound represented by formula (IA) (hereinafter sometimes referred to as "compound (IA)") and reacting compound (IA) with a sulfiding agent.

[0073] [ka]

[0074] In formula (IA), L, m, n, R 1 , and R 2 has the same meaning as in formula (I) above.

[0075] Compound (IA) can be obtained, for example, by a method including a step of reacting a compound represented by formula (II) (hereinafter, sometimes referred to as "compound (II)") with a compound represented by formula (III) (hereinafter, sometimes referred to as "compound (III)").

[0076] [ka]

[0077] In formula (II), n and R 1 has the same meaning as above.

[0078] [ka]

[0079] In formula (III), L, m, and R 2 has the same meaning as above, and X represents a leaving group.

[0080] The reaction of compound (II) with compound (III) 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 further preferably 0.1 to 3 mol, relative to 1 mol of compound (II).

[0081] In addition, two or more kinds of bases may be used in combination. When used in combination, it is preferable to use a combination of a carbonate such as sodium carbonate, potassium carbonate, lithium carbonate, or cesium carbonate, or a hydrogen carbonate such as sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, or cesium hydrogen carbonate, and a metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or cesium hydroxide, or a metal alkoxide such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium t-butoxide, or potassium t-butoxide, and more preferably a combination of a hydrogen carbonate and a metal hydroxide. When used in combination, two kinds may be added simultaneously or stepwise.

[0082] In compound (III), examples of the leaving group represented by X 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 compound (III) include epihalohydrin compounds (wherein L is a methylene group, m is 0, and R 2 is a hydrogen atom and X is a halogen atom). The amount of compound (III) used may be, for example, 0.01 to 20 moles, and preferably 0.5 to 15 moles, relative to 1 mole of compound (II). In this step, the reaction may be carried out using two or more kinds of compound (III).

[0083] The reaction between compound (II) and compound (III) 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.

[0084] 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.

[0085] The temperature for the reaction of compound (II) with compound (III) may be, for example, -80 to 200°C, preferably -40 to 150°C, more preferably -20 to 120°C, and further preferably -5 to 100°C.

[0086] In this manner, compound (IA) can be obtained. When using the obtained compound (IA) in the synthesis of compound (I), compound (IA) may be used after being isolated, or may be used as it is without being isolated.

[0087] Compound (I) can be obtained, for example, by a method including a step of reacting compound (IA) with a sulfurizing agent.

[0088] The reaction of compound (IA) with a sulfurizing agent is a reaction in which an oxygen atom of an epoxy ring or an oxetanyl ring of compound (IA) is replaced with a sulfur atom using a sulfurizing agent to form a thiirane ring (episulfide ring) or a thietane ring. Examples of the sulfurizing agent 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 arbitrarily according to the oxygen atom to be replaced. The amount of the sulfurizing agent used is, for example, 0.01 to 20 mol, preferably 0.5 to 10 mol, relative to 1 mol of compound (IA). In addition, by adjusting the amount of the sulfurizing agent used, the reaction temperature, the reaction time, etc., it is possible to replace both of the oxygen atoms in compound (IA) with sulfur atoms, or to replace one of the oxygen atoms in compound (IA) with a sulfur atom.

[0089] The reaction between compound (IA) and a sulfurizing agent is preferably carried out in a solvent. Examples of the solvent include the same solvents as those exemplified in the reaction between compound (II) and compound (III). The reaction between compound (IA) and a sulfurizing 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.

[0090] A polymerization inhibitor may be added to the reaction system to inhibit polymerization of the produced compound (I). 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, anhydrous nitric acid, anhydrous sulfuric acid, boron oxide, arsenic 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, 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, acetic acid, maleic acid, benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, salicylic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, benzoylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, 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 is converted into 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, phloroglucinone, 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. etc.

[0091] 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 further preferably 0.05 to 0.15 mol, relative to 1 mol of compound (I). 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.

[0092] The reaction product solution can be washed with an acidic aqueous solution to improve the stability over time of the obtained compound (I). Specific examples of the acid used in the acidic aqueous solution include the acids exemplified above as polymerization inhibitors. The acid may be used alone or in combination of two or more. The acidic aqueous solution usually tends to be effective at pH 6 or less, but is more effective at pH 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.

[0093] Furthermore, a hydrogen sulfide adsorbent can be used to improve the stability of compound (I). Examples of hydrogen sulfide adsorbents include iron (III) hydroxide, zinc oxide, KNK-301 (zinc oxide adsorbent, manufactured by Kureha Yushi Kogyo Co., Ltd.), Nionon 202A (iron oxide adsorbent, manufactured by Ibuki Seisakusho Co., Ltd.), and Limonic (iron hydroxide, 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.

[0094] The content of the component (A) may be, for example, 30 to 99% by mass based on the total amount of solids in the composition, since this makes it easy to obtain the effects of the present invention sufficiently. The content of the component (A) is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, based on the total amount of the composition, and is preferably 97% by mass or less, more preferably 95% by mass or less, and even more preferably 92% by mass or less.

[0095] The total amount of solids in the composition means the total amount of the 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 and gas chromatography. The content of each component in the solids of the composition may be calculated from the blending at the time of preparing the composition.

[0096] (B) Component: Compound (Z) The composition of the present embodiment contains component (B). Component (B) is a naphthalene compound having an iodine atom. By containing component (B), the composition can provide a cured product exhibiting a higher refractive index.

[0097] [ka]

[0098] In formula (Z), R i represents a monovalent substituent, R i If there are multiple, there are multiple R i may be the same or different. and p represents an integer of 1 to 8. q represents an integer of 0 to 7. However, the sum of p and q is 8 or less.

[0099] R i The monovalent substituent represented by R 2 Examples of the monovalent substituent include those similar to those represented by the following formula:

[0100] p represents an integer of 1 to 8. p is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0101] q represents an integer of 0 to 7. q is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 0.

[0102] The content of the (B) component may be, for example, 1 to 70% by mass based on the total amount of solids in the composition, since the effects of the present invention can be sufficiently obtained. The content of the (B) component is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more, based on the total amount of the composition, and is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

[0103] Component (C): Polymerization initiator The composition may contain one or more (C) components. The (C) component is not particularly limited as long as it can initiate the polymerization of the (A) component, and examples thereof include radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, radical and cationic polymerization initiators, etc. The radical polymerization initiators, cationic polymerization initiators, and anionic polymerization initiators generate radicals, acids, or bases, respectively, by at least one of active energy ray irradiation and heat, and cause radical polymerization, cationic polymerization, or anionic polymerization of the (A) component to proceed. Note that the (A) component can be polymerized and cured by at least one of active energy ray irradiation and heat, even in the absence of a polymerization initiator.

[0104] Examples of thermal radical polymerization initiators that initiate radical polymerization by heat include organic peroxides such as hydrogen peroxide and perbenzoic acid, and azo compounds such as azobisbutyronitrile, etc. Examples of photoradical polymerization initiators that initiate radical polymerization by irradiation with active energy rays include oxime compounds, alkylphenone compounds, aryl ketone compounds, biimidazole compounds, triazine compounds, acylphosphine compounds, etc.

[0105] A cationic polymerization initiator is a compound capable of releasing a substance that initiates cationic polymerization by at least one of active energy ray irradiation and heat. Examples of cationic polymerization initiators include aromatic iodonium salts, aromatic sulfonium salts, aromatic ammonium salts, and cyclopentadienyl iron (II) complexes. These can initiate cationic polymerization by at least one of active energy ray irradiation and heat depending on the difference in structure. A compound capable of releasing a substance that initiates cationic polymerization by active energy ray irradiation is called a photo-cationic polymerization initiator, and a compound capable of releasing a substance that initiates cationic polymerization by heat is called a thermal cationic polymerization initiator.

[0106] An anionic polymerization initiator is a compound capable of releasing a substance that initiates anionic polymerization by at least one of active energy ray irradiation and heat. Examples of anionic polymerization initiators include ammonium salts, DBU (diazabicycloundecenium) salts, DBN (diazabicyclononenium) salts, biguanidium salts, aromatic phosphonium salts, aromatic dimethylurea, and aliphatic dimethylurea. These can initiate anionic polymerization by at least one of active energy ray irradiation and heat depending on the difference in structure. A compound capable of releasing a substance that initiates anionic polymerization by active energy ray irradiation is called a photoanionic polymerization initiator, and a compound capable of releasing a substance that initiates anionic polymerization by heat is called a thermal anionic polymerization initiator.

[0107] When the composition contains the component (C), from the viewpoint of improving the heat resistance of the composition and a cured product thereof, the composition preferably contains a thermal cationic polymerization initiator or a thermal anionic polymerization initiator, and more preferably contains a thermal anionic polymerization initiator.

[0108] When the composition contains the component (C), the content of the polymerization initiator, relative to 100 parts by mass of the total amount of the component (A) and the curable compounds other than the component (A), is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, from the viewpoint of improving the curability and / or heat resistance, and is preferably 10 parts by mass or less, and more preferably 8 parts by mass or less, from the viewpoint of improving the physical properties such as the mechanical properties of the cured product.

[0109] Component (D): Polymerization inhibitor The composition may contain one or more (D) components. Whether or not to contain a polymerization inhibitor in the composition is preferably determined, for example, taking into consideration the type of (C) component. The (C) component is preferably dissolved or dispersed in a solvent. The (D) component contained in the composition may be added during the preparation of the composition, or may be added after the production of the (A) component. By containing the (D) component in the composition, unintended polymerization of the (A) component is suppressed, and the storage stability of the composition can be improved.

[0110] Examples of component (D) include the same polymerization inhibitors that are added to the reaction system to inhibit the polymerization of the produced compound (I), and are preferably formic acid or acetic acid.

[0111] When the composition contains the (D) component, from the viewpoint of improving the storage stability of the composition, the content of the (D) component, per 100 parts by mass of the total amount of the (A) component, 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, 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.

[0112] Examples of other components contained in the composition include resins, curable compounds other than component (A), solvents, additives, etc. Examples of additives include inorganic particles, fillers, polymerization initiators, sensitizers, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, ultraviolet absorbers, antioxidants, dispersants, etc.

[0113] (resin) The composition may contain one or more resins. By containing a resin in the composition, it is possible to impart developability to the 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 the resin 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.

[0114] Examples of the thermoplastic resin include olefin resins such as polyethylene resin, polypropylene resin, and polycycloolefin resin; (meth)acrylic resins such as poly(meth)acrylic acid ester resin; 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; polyphenylene sulfide resin, etc. One or more of these resins may be used as a polymer blend or polymer alloy.

[0115] Examples of the curable resin include resins having a photopolymerizable group or a thermally polymerizable group, more specifically, (meth)acrylic resins, epoxy resins, melamine resins, unsaturated polyester resins, phenol resins, urea resins, alkyd resins, polyimide resins, and the like.

[0116] Other examples of the resin include an alkali-soluble resin. By containing an alkali-soluble resin in the composition, it is possible to impart developability to the cured product of the composition. The alkali-soluble resin means a resin that is soluble in an aqueous alkaline solution. Specifically, for example, a resin having a carboxyl group and / or a phenolic hydroxyl group can be mentioned.

[0117] From the viewpoint of improving the developability and solvent resistance of the cured product of the composition, the acid value of the alkali-soluble resin is preferably 10 to 170 mgKOH / g, more preferably 20 to 150 mgKOH / g, and further preferably 30 to 140 mgKOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the alkali-soluble resin, and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

[0118] 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.

[0119] The weight average molecular weight (Mw) of the resin, calculated based on standard polystyrene, measured by gel permeation chromatography (GPC) may be, for example, 5 to 2 million, preferably 1,000 to 1 million, and more preferably 1,500 to 750,000. The Mw of the resin can be adjusted by appropriately combining reaction conditions such as the selection of raw materials used, the charging method, the reaction temperature, and the time.

[0120] 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.

[0121] ((A) Curable Compound Other Than Component (Compound (I))) The composition may contain one or more curable compounds other than the component (A). By containing a curable compound other than the component (A), the viscosity or curability of the composition can be adjusted, and the mechanical properties and / or optical properties of the obtained cured product and a molded product containing the same can be adjusted.

[0122] Examples of the curable compound other than component (A) include episulfide (thiirane) compounds other than component (A), thietane compounds other than component (A), 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, (meth)acrylate compounds, and acid anhydrides.

[0123] When the composition contains a curable compound other than the component (A), the content of the curable compound other than the component (A) is preferably 1 mass % or more, more preferably 2 mass % or more, based on the total amount of solids in the composition, and is preferably 30 mass % or less, more preferably 20 mass % or less.

[0124] (solvent) The composition may contain one or more solvents. The solvent is preferably one that can dissolve or disperse the component (A), and more preferably one that can further dissolve or disperse other components other than the component (A). As the solvent, for example, the solvent (organic solvent) exemplified in the reaction between compound (II) and compound (III) can be used.

[0125] 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 amount of solids in the composition. When the composition contains a solvent, the solids concentration of the composition is preferably 5 to 60% by mass, more preferably 10 to 50% by mass.

[0126] <Cured products and molded products> The cured product of one embodiment is a cured product of the composition. The molded product of one embodiment is obtained by curing the composition, and includes a cured product of the composition. The composition has excellent film-forming properties, curing properties, etc., and 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 the component (A) in the composition by at least one of irradiation with active energy rays and heat. The shape of the molded product containing the cured product is not particularly limited, and may include a film (membrane), plate, lens, powder, granule, non-spherical particle, crushed particle, porous, chunky continuous body, fiber, tube, hollow fiber, etc., and may be any shape depending on the application of the molded product.

[0127] 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.

[0128] In the cast polymerization molding method, for example, the composition is injected into a mold, degassed as necessary, cured by heating in an oven, etc., and the obtained molded product is removed. The molded product thus removed can also be irradiated with active energy rays for additional curing.

[0129] When forming a film as a molded product on a substrate, the composition is applied to the substrate, and dried as necessary 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). The patterned cured film can be obtained by patterning using a method such as a photolithography method, an inkjet method, or a printing method. The patterning method may be, for example, a photolithography method. The photolithography method is a method in which the composition is applied to a substrate, and dried as necessary to form a coating film (coating layer), the coating film (coating layer) is exposed through a photomask, and the coating film (coating layer) after exposure is developed.

[0130] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass with a silica-coated surface, 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.

[0131] The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, from light with wavelengths in this range, light with wavelengths around 436 nm, around 408 nm, or around 365 nm may be selectively extracted by a bandpass filter according to the absorption wavelength of the photopolymerization initiator. Specific examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp. After the pattern exposure, the exposed coating film (coating layer) may be heated before development (pre-development bake).

[0132] The developer used for development may be, for example, an aqueous solution or solvent containing an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide. As the solvent, for example, the solvent (organic solvent) exemplified in the reaction between compound (II) and compound (III) may be used. 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).

[0133] Since 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 refractive index by adjusting the composition of the composition. 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.

[0134] The refractive index at a wavelength of 550 nm of the 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 on which a cured film is formed. Next, a transmission spectrum and a reflection spectrum at wavelengths of 300 nm to 800 nm are measured for the substrate on which the cured film is formed using a visible-ultraviolet spectrophotometer (e.g., "V-650" manufactured by JASCO Corporation) equipped with an integrating sphere unit (e.g., "ISV-922" manufactured by JASCO Corporation). Next, from the true reflection spectrum obtained by subtracting the increase or decrease due to interference in the reflection spectrum from the transmission spectrum and the reflection spectrum and smoothing it, the refractive index at a wavelength of 550 nm of the cured product or a molded product containing the same is calculated based on the Fresnel formula (e.g., Hecht Optics I Original 5th Edition, Maruzen Publishing, 2018, p.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 obtained.

[0135] <Usage> Applications of the cured or molded products include, for example, glass substitutes and surface coating materials thereof; coating materials for window glass, lighting glass, and light source protection glass for residences, facilities, transportation equipment, etc.; window films for residences, facilities, transportation equipment, etc.; interior and exterior materials and interior and exterior paints for residences, 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 light sources that emit ultraviolet rays, such as fluorescent lamps and mercury lamps; components for precision machinery, electronic and electrical equipment, and materials for blocking electromagnetic waves generated by 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 matter, dyed matter, dyes and pigments, etc.; protective films for polymer supports (for example, for plastic parts of machines and automobile 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, hair products, etc.; clothing textiles and fibers such as sportswear, stockings, hats, etc.; household interior items such as curtains, carpets, wallpaper, etc.; medical devices such as plastic lenses, contact lenses, artificial eyes, etc.; 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, photographic materials, etc.; stationery such as mold films, transfer stickers, anti-graffiti films, tapes, inks, etc.; sign boards, markers, etc. and their surface coating materials; substrates used in optical devices, etc.; optical waveguides; holograms; LED encapsulants, etc.

[0136] The molded article is suitably used as a lens, which is an optical component used in an optical device. Examples of the optical device include a solid-state imaging element and a display device. In a solid-state imaging element, a lens is used for improving the efficiency of collecting light on each photoelectric conversion element. In a display device, a lens is used for improving the efficiency of extracting light from a pixel. The lens may be a microlens. Examples of the display device include a liquid crystal display device and an organic EL display device.

[0137] 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, it may not be easy to mold the product, for example, etching may not proceed easily, and the high refractive index material may scatter during molding, causing contamination problems. Such problems can be solved by using the high refractive index material of the present embodiment, which is an organic compound.

[0138] The cured product of the composition of this embodiment can be suitably used as a main chain cleavage type positive resist. In the formation of a resist pattern using the cured product of the composition of this embodiment, the main chain of the polymer of component (A) constituting the cured product is cleaved in the irradiated part of the resist film by irradiation with ionizing radiation or the like (for example, electron beam, KrF laser, ArF laser, EUV laser, etc.), resulting in low molecular weight. Therefore, a difference in solubility in a developer occurs between the exposed part and the unexposed part, and a resist pattern is formed. The resist pattern using the cured product of the composition of this embodiment can be applied when forming a resist pattern in the manufacture of printed circuit boards such as build-up boards, semiconductors, photomasks, molds, etc. EXAMPLES

[0139] 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.

[0140] [Synthesis Example 1] <Synthesis of compound (I-1)> Synthesis of compound (I-A1) [ka]

[0141] A four-neck flask equipped with a Dimroth condenser and a thermometer was filled with nitrogen, 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. Then, 15 parts of sodium hydroxide, 66 parts of acetone, and 203 parts of pure water were added to another flask and completely dissolved, and then the mixture was 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 (I-A1) (compound (I-A1)).

[0142] 1 H-NMR analysis and LC-MS measurement confirmed that compound (I-A1) 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

[0143] Synthesis of compound (I-1) [ka]

[0144] A four-neck flask equipped with a Dimroth condenser and a thermometer was filled with nitrogen, and 3 parts of compound (I-A1), 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 (I-1) (compound (I-1)).

[0145] 1 H-NMR analysis and LC-MS measurement confirmed that compound (I-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

[0146] [Examples 1 to 6, Comparative Examples 1 to 4, and Reference Examples 1 and 2] <Preparation of Composition> The ingredients shown in Table 1 were added to a flask in the amounts (unit: parts by mass) shown in Table 1 and stirred to prepare liquid compositions of Examples 1 to 6, Comparative Examples 1 to 4, and Reference Examples 1 and 2. The compositions of Examples 1 to 6, Reference Examples 1 and 2, and Comparative Examples 1 and 3 were transparent when observed with the naked eye, and it was confirmed that the ingredients were uniformly dissolved. The compositions of Comparative Examples 2, 4, and 5 were cloudy when observed with the naked eye, and it was confirmed that the ingredients were not uniformly dissolved.

[0147] The details of the abbreviations of the ingredients shown in Table 1 are as follows. (A) Component: Sulfur-containing heterocyclic compound (A-1): Compound (I-1) synthesized in Synthesis Example 1 (B) Component: Compound (Z) (B-1): A compound represented by formula (B-1) [ka] Component (C): Polymerization initiator (C-1): DBN (diazabicyclononenium) salt type thermal anionic polymerization initiator (manufactured by San-Apro Co., Ltd., "U-CAT 1102") (C-2): Ammonium salt type thermal cationic polymerization initiator (KING INDUSTRIES INC., "CXC-1821") Curable compounds other than component (A) Compound (Y1): A compound represented by formula (Y1) (1,6-bis(glycidyloxy)naphthalene, manufactured by DIC Corporation, "EPICLON HP-4032D") [ka] Compound (Y2): A compound represented by formula (Y2) (bisphenol A diglycidyl ether, manufactured by DIC Corporation, "EPICLON EXA-850CRP") [ka] Compound (Y3): A compound represented by formula (Y3) (2,2'-diglycidyloxy-1,1'-binaphthalene, Sugai Chemical Industry Co., Ltd., "DGOBINL") [ka] Compound (Y4): A compound represented by formula (Y4) (9-vinylcarbazole, manufactured by Tokyo Chemical Industry Co., Ltd.) [ka] solvent Solvent (E-1): Cyclopentanone

[0148] The compound represented by formula (B-1) was synthesized with reference to J. Phys. Chem. A 2003, 107, 480-484.

[0149] <Evaluation test> (1) Film formability For the compositions of Examples 1 to 6, Comparative Examples 1 to 4, and Reference Examples 1 and 2, 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 (thickness 0.7 mm, Corning Incorporated, "Eagle XG"), and spin-coated at 1000 rpm for 20 seconds using a spin coater (Mikasa Co., Ltd., "MS-B100") to form a coating film. The alkali-free glass plate on which the coating film was formed was heated at 60°C for 2 minutes to remove the solvent.

[0150] The obtained coating film was observed, and the film-forming property of the composition was evaluated according to the following evaluation criteria. The results are shown in Table 1. The hole defect means a state in which a hole having a diameter of 1 mm or more is formed in the coating film, and the non-alkali glass plate is exposed. If the result is A, it can be said that the film-forming property is good. A: Colorless and transparent, with neither hole defects nor cloudiness observed. D1: There was a hole defect. D2: It was cloudy.

[0151] The compositions of Examples 1 to 6, Comparative Examples 1 and 2, and Reference Examples 1 and 2 that were evaluated as "A" and "D1" in (1) were evaluated below.

[0152] (2) Formation of hardened film About 3 mL of each of the compositions of Examples 1 to 6, Comparative Examples 1 and 2, and Reference Examples 1 and 2 was dropped onto an alkali-free glass plate (thickness 0.7 mm, 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 was formed was heated at 60°C for 2 minutes to remove the solvent. Next, the alkali-free glass plate on which the coating film was formed was post-baked by heating 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 was measured using a stylus-type film thickness gauge (Bruker, "DekTak XT"), and all of the thicknesses were 1.5 μm.

[0153] (3) Refractive index measurement The non-alkali glass on which the cured film was formed, prepared in (2) above, was used to measure the transmission spectrum and reflection spectrum at wavelengths of 300 nm to 800 nm using a visible-ultraviolet spectrophotometer (manufactured by JASCO Corporation, "ISV-922") equipped with an integrating sphere unit (manufactured by JASCO Corporation, "V-650"). The true reflection spectrum obtained by subtracting the increase or decrease due to interference in the reflection spectrum from the transmission spectrum and reflection spectrum and smoothing it was calculated from the value at a wavelength of 550 nm and the refractive index of the non-alkali glass plate (manufactured by Corning, "Eagle XG") based on Fresnel's formula (Hecht Optics I Original 5th Edition, Maruzen Publishing, 2018, p.209-226). The results are shown in Table 1.

[0154] [Table 1]

[0155] As shown in Table 1, the compositions of the examples were superior in terms of film-forming properties and refractive index to the compositions of the comparative examples. These results confirmed that the compositions of the present invention can provide cured products exhibiting high refractive index without impairing film-forming properties.

Claims

1. A composition comprising: (A) a compound having at least one thiirane group or thietane group; and (B) a compound represented by formula (Z). 【Chemistry 1】 [In formula (Z), R ｉ represents a monovalent substituent, R ｉ If there are multiple R ｉ may be the same or different. p represents an integer of 1 to 8. q represents an integer of 0 to 7. However, the sum of p and q is 8 or less.

2. The composition according to claim 1 , further comprising (C) a polymerization initiator.

3. The composition of claim 1 further comprising (D) a polymerization inhibitor.

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

5. A molded article obtained by curing the composition according to any one of claims 1 to 4.

6. A cured product of the composition according to any one of claims 1 to 4.

7. A display device comprising the cured product according to claim 6.

8. A solid-state imaging device comprising the cured product according to claim 6 .

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