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

Abstract

The invention relates to a composition, a cured product thereof, a molded product, a display device, and a solid-state imaging device. The present invention addresses the problem of providing a composition capable of supplying a cured product exhibiting a high refractive index without impairing film-forming properties. The solution of the present invention is a composition containing: (A) a compound having at least one thiirane group or thietanyl group; and (B) a compound represented by formula (Z). In formula (Z), Ri represents a monovalent substituent, and if a plurality of Ri are present, the plurality of Ri may be the same as or different from each other. And p represents an integer of 1-8. And q represents an integer of 0-7. Wherein the sum of p and q is 8 or less. # imgabs0 #

Description

Technical Field

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

[0002] In the field of optical equipment, high refractive materials are eagerly desired. By using high refractive materials, lenses can be obtained, and the optical path in the optical equipment can be controlled by the lenses. In solid-state imaging devices, lenses are used for the purpose of improving the efficiency of focusing light into each photoelectric conversion element. In display devices, lenses are used for the purpose of improving the efficiency of extracting light from pixels. In the past, various high refractive materials have been developed, and it is known to add inorganic fillers for high refractive. On the other hand, there are also cases where the addition of inorganic fillers causes various problems, such as light scattering caused by agglomeration of inorganic fillers and surrounding pollution caused by metal ions during processing. As a previous high refractive material, for example, a composition containing a specific (meth)acrylate compound is known (for example, Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2011 / 102258 Summary of the invention

[0006] Problems to be solved by the invention

[0007] A main object of the present invention is to provide a composition capable of providing a cured product having a high refractive index without impairing film-forming properties.

[0008] Means for solving problems

[0009] The present invention provides the composition described in [1] to [4], the molded product described in [5], the cured product described in [6], the display device described in [7], and the solid-state imaging device described in [8].

[0010] [1] A composition comprising: (A) a compound having at least one thiirane group or thietanyl group; and (B) a compound represented by the formula (Z).

[0011]

[0012] [In formula (Z),

[0013] R i represents a monovalent substituent, R i There are multiple cases where there are multiple R i Can be the same or different.

[0014] p represents an arbitrary integer from 1 to 8.

[0015] q represents an arbitrary integer from 0 to 7.

[0016] Wherein, the sum of p and q is less than 8.]

[0017] [2] The composition according to [1], further comprising (C) a polymerization initiator.

[0018] [3] The composition according to [1] or [2], further comprising (D) a polymerization inhibitor.

[0019] [4] The composition according to any one of [1] to [3], wherein (A) the compound having at least one thiirane group or thietanyl group is a compound represented by formula (I).

[0020]

[0021] [In formula (I),

[0022] L represents a single bond or a divalent group, and two L's present may be the same or different.

[0023] A 1 Represents oxygen or sulfur atoms, with two A 1 They can be the same or different. Among them, there are two A 1 At least one of them is a sulfur atom.

[0024] m represents 0 or 1, and two m's may be the same or different.

[0025] n represents an arbitrary integer from 0 to 6.

[0026] R 1 represents a monovalent substituent, R 1 There are multiple cases where there are multiple R 1 Can be the same or different.

[0027] R 2 represents a hydrogen atom or a monovalent substituent, and there are two R 2 Can be the same or different.]

[0028] [5] A molded article formed by curing the composition according to any one of [1] to [4].

[0029] [6] A cured product of the composition according to any one of [1] to [4].

[0030] [7] A display device comprising the cured product described in [6].

[0031] [8] A solid-state imaging device comprising the cured product described in [6].

[0032] Effects of the Invention

[0033] According to the present invention, a composition that can supply a cured product showing a high refractive index without damaging film-forming properties can be provided. In addition, according to the present invention, 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 can be provided. DETAILED DESCRIPTION

[0034] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0035] In this specification, the numerical range shown by "~" indicates a range including the numerical values ​​recorded before and after "~" as the minimum value and the maximum value, respectively. In the numerical range recorded in stages in this specification, the upper limit value or lower limit value recorded in one numerical range can be replaced by the upper limit value or lower limit value of the numerical range recorded in other stages. In addition, in the numerical range recorded in this specification, the upper limit value or lower limit value of the numerical range can be replaced by the value shown in the embodiment.

[0036] In this specification, (meth)acrylate refers to acrylate or its corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl, (meth)acrylate, etc.

[0037] In this specification, as for the materials exemplified below, unless otherwise specified, within the scope of meeting the conditions, one kind may be used alone, or two or more kinds may be used in combination. As for the content of each component, when there are multiple substances belonging to each component, unless otherwise specified, it refers to the total amount of the multiple substances.

[0038] <Composition>

[0039] The composition of one embodiment contains (A) a compound having at least one thiirane group or thietanyl group (hereinafter, sometimes referred to as a "sulfur-containing heterocyclic compound"), and (B) a compound represented by formula (Z) (hereinafter, sometimes referred to as "compound (Z)". According to the composition of this embodiment, a cured product showing a high refractive index can be provided without impairing film-forming properties. The composition of this embodiment may further contain (C) a polymerization initiator, (D) a polymerization inhibitor, etc.

[0040] (A) Ingredients: Sulfur-containing heterocyclic compounds

[0041] The composition of the present embodiment contains component (A). Component (A) may be a curable compound. Since the composition contains component (A), component (A) is polymerized to provide a cured product showing a high refractive index. The composition containing component (A) also has excellent film-forming properties.

[0042] The component (A) may be used without particular limitation as long as it is a compound having at least one thiirane group or thietanyl group. For example, the component (A) may be a compound having at least one group represented by the formula (X0), preferably a compound having at least one group represented by the formula (X1).

[0043]

[0044] In formula (X0),

[0045] m represents 0 or 1.

[0046] R 2 represents a hydrogen atom or a monovalent substituent.

[0047] *Indicates bonding position.

[0048]

[0049] In formula (X1),

[0050] L represents a single bond or a divalent group.

[0051] m represents 0 or 1.

[0052] R 2 represents a hydrogen atom or a monovalent substituent.

[0053] *Indicates bonding position.

[0054] Examples of the divalent group represented by L include a divalent aliphatic chain hydrocarbon group which may have a substituent; a divalent alicyclic hydrocarbon group which may have a substituent; a divalent aromatic hydrocarbon group which may have a substituent; a divalent group formed by a combination of these (e.g., aralkylene) and the like. The methylene group (-CH2-) contained in the divalent group may be -O-, -S-, -NR- A -(R A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ), -CO-, or -SO2-.

[0055] As the divalent aliphatic chain hydrocarbon group, for example, a saturated or unsaturated aliphatic chain hydrocarbon group can be mentioned. More specifically, alkane diyls such as methylene, ethylene, propane diyl, butane diyl, pentane diyl, hexane diyl, heptane diyl, octane diyl, nonane diyl, decane diyl, undecane diyl, dodecane diyl, tridecane diyl, tetradecane diyl, pentadecane diyl, hexadecane diyl, heptadecanediyl, octadecane diyl, nonadecanediyl, and eicosane diyl can be mentioned. The divalent aliphatic chain hydrocarbon group can be straight-chain 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, further preferably 1 to 4, and particularly preferably 1 or 2.

[0056] Examples of the substituent which the divalent aliphatic chain hydrocarbon group may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; an amino group; an acetyl group; a cyano group, and the like.

[0057] Examples of the divalent alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups. More specifically, 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.

[0058] Examples of substituents 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; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; hydroxyl; amino; acetyl; cyano, and the like.

[0059] The divalent aromatic hydrocarbon group may be monocyclic or polycyclic. Examples of the divalent aromatic hydrocarbon group include phenylene, naphthylene, anthracenediyl, fluorenediyl, etc. The number of carbon atoms in the divalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0060] Examples of substituents 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 atoms; hydroxyl; amino; acetyl; cyano, and the like.

[0061] As R 2 The monovalent substituent represented by , for example, may include 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, a monovalent group formed by a combination of these (for example, an aralkyl group), etc.; a hydroxyl group; an amino group which may be substituted with 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, a methylethylamino group, etc.; a heterocyclic group such as an aliphatic heterocyclic group having 4 to 20 carbon atoms, or an aromatic heterocyclic group having 3 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, a furyl group, etc.; a halogen atom; a nitro group; a cyano group; a carboxyl group; a sulfone group; a thiol group; a formyl group; an -SF3 group; and a -SF5 group. The methylene group (-CH2-) contained in the monovalent substituent can be replaced by -O-, -S-, -NR B -(R B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ), -CO-, or -SO2-. It should be noted that the group obtained by replacing the methylene group (-CH2-) contained in the monovalent substituent with -O- includes alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, and alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, and methoxyethyl.

[0062] As the monovalent aliphatic chain hydrocarbon group, for example, a saturated or unsaturated aliphatic chain hydrocarbon group can be mentioned. 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, eicosyl and the like can be mentioned. The monovalent aliphatic chain hydrocarbon group can be straight-chain 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, further preferably 1 to 4, and particularly preferably 1 or 2.

[0063] Examples of the substituent which the monovalent aliphatic chain hydrocarbon group may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; an amino group; an acetyl group; a cyano group, and the like.

[0064] 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, 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.

[0065] Examples of substituents 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; halogen atoms such as fluorine, chlorine, bromine and iodine atoms; hydroxyl; amino; acetyl; cyano and the like.

[0066] The monovalent aromatic hydrocarbon group may be a monocyclic or polycyclic group. Examples of the monovalent aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, fluorenyl, etc. The number of carbon atoms in the monovalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0067] Examples of substituents 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 atoms; hydroxyl; amino; acetyl; cyano, and the like.

[0068] m represents 0 or 1. When m is 0, it represents a three-membered ring structure as a thiirane group, and when m is 1, it represents a four-membered ring structure as a thielane group. m is preferably 0.

[0069] From the viewpoint of the high refractive index of the cured product, component (A) is preferably a compound containing an aromatic ring. As the aromatic ring, there can be mentioned aromatic hydrocarbon rings of benzene ring, naphthalene ring, anthracene ring; aromatic heterocyclic rings such as furan, pyrrole, benzofuran, thiophene, benzothiophene, indole, pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, triazine, etc. The aromatic ring is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring.

[0070] From the viewpoint of a high refractive index of a cured product, the component (A) is preferably a compound represented by the formula (I).

[0071]

[0072] In formula (I),

[0073] L represents a single bond or a divalent group, and two L's present may be the same or different.

[0074] A 1 Represents oxygen or sulfur atoms, with two A 1 They can be the same or different. Among them, there are two A 1 At least one of them is a sulfur atom.

[0075] m represents 0 or 1, and two m's may be the same or different.

[0076] n represents an arbitrary integer from 0 to 6.

[0077] R 1 represents a monovalent substituent, R 1 There are multiple cases where there are multiple R 1 Can be the same or different.

[0078] R 2 represents a hydrogen atom or a monovalent substituent, and there are two R 2 Can be the same or different.

[0079] L means the same as above, m means the same as above, R 2 Indicates the same meaning as above.

[0080] In compound (I), there are two groups represented by formula (X) that can be bonded to any position of 1 to 8 of the naphthalene ring. The group represented by formula (X) on the naphthalene ring can be bonded to any two positions of 1 to 4 (5 to 8), or to any one of 1 to 4 (5 to 8) and any one of 5 to 8 (1 to 4). The group represented by formula (X) on the naphthalene ring is preferably bonded to any one of 1 to 4 (5 to 8) and any one of 5 to 8 (1 to 4).

[0081]

[0082] In formula (X), L, A 1 , m, and R 2 has the same meaning as above, and * indicates a bonding position.

[0083] In compound (I) having one or more R 1 In the case of a monovalent substituent represented by 1 The monovalent substituent represented by may be bonded to any position of the 1-8 positions of the naphthalene ring except the bonding position of the group represented by formula (X).

[0084] L represents a single bond or a divalent group, and two Ls present may be the same or different, and may be the same. In compound (I), when there are two Ls, it is preferred that at least one is an alkanediyl group, and it is more preferred that 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, further preferably 1 to 4, and particularly preferably 1 or 2.

[0085] A 1 Represents oxygen or sulfur atoms, with two A 1 They can be the same or different. Among them, there are two A 1 At least one of them is a sulfur atom. In compound (I), there are two A 1 As for A, preferably both are sulfur atoms. 1 The number of sulfur atoms increases, and a cured product having a higher refractive index can be provided, and there is a tendency for film-forming properties to be more excellent.

[0086] m represents 0 or 1. Two m's present may be the same or different, and may be the same. In compound (I), it is preferred that both of the two m's present are 0.

[0087] 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.

[0088] R 1 represents a monovalent substituent, R 1 There are multiple cases where there are multiple R 1 Can be the same or different, can be the same. 1 The monovalent substituent represented by R can be exemplified by 2 The monovalent substituent represented by is the same substituent as that represented by .

[0089] R 2 represents a hydrogen atom or a monovalent substituent, and there are two R 2 In compound (I), there are two R 2 It 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, further 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.

[0090] Examples of the component (A) (compound (I)) include compounds represented by formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), and formula (If). In formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), and formula (If), L and A 1, m, n, R 1 , and R 2 Indicates the same meaning as above.

[0091]

[0092] In formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), and formula (If), when there are two L, at least one is preferably an alkanediyl group, and both are more preferably alkanediyl groups. In this case, the number of carbon atoms in the alkanediyl group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 or 2.

[0093] In formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), and formula (If), there are two m, each of which is independently 0 or 1, preferably 0. In formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), and formula (If), there are two m, both of which are 0.

[0094] In formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), and formula (If), n is each independently any integer from 0 to 6, preferably any integer from 0 to 3, more preferably any integer from 0 to 2, further preferably 0 or 1, and particularly preferably 0.

[0095] In formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), and formula (If), there are two A 1 Each independently represents an oxygen atom or a sulfur atom. 1 At least one of A is a sulfur atom. 1 In particular, both are preferably sulfur atoms.

[0096] In formula (Ia), formula (Ib), formula (Ic), formula (Id), formula (Ie), and formula (If), there are two R 2 Each is independently preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group, more preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group having 1 to 6 carbon atoms, further 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 Preferably the same.

[0097] Specific examples of the component (A) (compound (I)) are shown below, but the present invention is not limited to these.

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105] 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.

[0106] The compound (I) as the component (A) can be obtained by synthesizing a compound represented by the formula (IA) (hereinafter, sometimes referred to as "compound (IA)") and reacting the compound (IA) with a sulfiding agent.

[0107]

[0108] In formula (IA), L, m, n, R 1 , and R 2 It has the same meaning as the above (Formula (I)).

[0109] Compound (IA) can be obtained, for example, by a method comprising the 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)".

[0110]

[0111] In formula (II), n and R 1 Indicates the same meaning as above.

[0112]

[0113] In formula (III), L, m, and R 2 represents the same meaning as above, and X represents a leaving group.

[0114] The reaction of compound (II) and compound (III) can be carried out 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 bicarbonate, potassium bicarbonate, lithium bicarbonate, and cesium bicarbonate; metal alkoxides such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium tert-butoxide, and potassium tert-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-lutidine, 2,6-di-tert-butylpyridine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, and tetramethylammonium chloride. The amount of the base to be 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, based on 1 mol of compound (II).

[0115] In addition, alkali can also be used in combination with more than two kinds of alkali. In the case of use in combination, preferably carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate or bicarbonates such as sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, and metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide or sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium tert-butoxide, potassium tert-butoxide, more preferably a combination of bicarbonate and metal hydroxide. In the case of use in combination, two kinds can be added simultaneously, or they can be added in stages.

[0116] In compound (III), as the leaving group represented by X, there can be mentioned halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, trifluoromethylsulfonyl, perfluoroethylsulfonyl, perfluoropropylsulfonyl, perfluorobutylsulfonyl; arylsulfonyl groups such as phenylsulfonyl, p-toluenesulfonyl, p-fluorophenylsulfonyl, pentafluorophenylsulfonyl, etc. Specific examples of compound (III) include epihalohydrin compounds (L is methylene, m is 0, R is 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 mol, preferably 0.5 to 15 mol, relative to 1 mol of compound (II). In this step, two or more compounds (III) may be used to carry out the reaction.

[0117] The reaction of compound (II) and compound (III) is preferably carried out in a solvent. As the solvent, in addition to water, organic solvents such as ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, alcohols, glyme, esters, aliphatic nitriles, sulfoxides, and amides can be cited. As the organic solvent, the following solvents can be exemplified.

[0118] 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.

[0119] Aromatic hydrocarbons: benzene, toluene, xylene, mesitylene, naphthalene, anisole, nitrobenzene, aniline, tetralin, durene, etc.

[0120] Halogenated aromatic hydrocarbons: chlorobenzene, dichlorobenzene, chloronaphthalene, etc.

[0121] Aliphatic hydrocarbons: pentane, hexane, heptane, etc.

[0122] Halogenated aliphatic hydrocarbons: dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, tetrachloroethylene, etc.

[0123] Ethers: diethyl ether, diisopropyl ether, methyl tert-butyl ether, cyclopentyl methyl ether, diphenyl ether, dimethoxyethane, dioxane, etc.

[0124] Alcohols: methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, hexafluoroisopropanol, etc.

[0125] Glyme: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, etc.

[0126] Esters: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc.

[0127] Aliphatic nitriles: acetonitrile, etc.

[0128] Sulfoxides: dimethyl sulfoxide, sulfolane, etc.

[0129] Amides: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0130] The temperature for the reaction of compound (II) and 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.

[0131] By operating as described above, compound (IA) can be obtained. When the obtained compound (IA) is used in the synthesis of compound (I), compound (IA) may be used after isolation or may be used directly without isolation.

[0132] Compound (I) can be obtained, for example, by a method comprising the step of reacting compound (IA) with a sulfiding agent.

[0133] The reaction of compound (IA) with a vulcanizing agent is a reaction in which the oxygen atom of the epoxy ring or the oxetanyl ring of compound (IA) is replaced with a sulfur atom using a vulcanizing agent to form a thiirane ring (epithelial ring) or a thietane ring. Examples of the vulcanizing agent include thiourea, methylthiourea, dimethylthiourea, trimethylthiourea, tetramethylthiourea, tetraethylthiourea, ethylenethiourea, phenylthiourea, diphenylthiourea, tolylthiourea, xylylthiourea, sodium thiocyanate, potassium thiocyanate, and the like. The amount of the vulcanizing agent used can be arbitrarily adjusted depending on the oxygen atom to be replaced. The amount of the vulcanizing agent used is, for example, 0.01 to 20 moles, preferably 0.5 to 10 moles, relative to 1 mole of compound (IA). In addition, by adjusting the amount of the vulcanizing agent used, the reaction temperature, the reaction time, and the like, two oxygen atoms in compound (IA) can be replaced with sulfur atoms, or one oxygen atom in compound (IA) can be replaced with a sulfur atom.

[0134] The reaction of compound (IA) with a sulfiding agent is preferably carried out in a solvent. Examples of the solvent include the same solvents as those exemplified in the reaction of compound (II) with compound (III). The reaction of compound (IA) with a sulfiding agent may be carried out at, for example, -80 to 200°C, preferably -40 to 100°C, more preferably -20 to 80°C, and even more preferably -5 to 60°C.

[0135] In order to inhibit the polymerization of the generated compound (I), a polymerization inhibitor may be added to the reaction system. Examples of polymerization inhibitors include acids and acid anhydrides. More specifically, examples include:

[0136] Inorganic acidic compounds such as nitric acid, hydrogen chloride (hydrochloric acid), perchloric acid, hypochlorous acid, chlorine dioxide, hydrofluoric acid, sulfuric acid, oleum, sulfonyl 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, silicon dioxide, aluminum oxide, 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;

[0137] 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, octanoic acid, cycloalkane 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-naphthoic acid, β-naphthoic acid, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and trifluoroacetic anhydride;

[0138] Phosphoric acids such as mono-, di- and tri-methyl phosphate, mono-, di- and tri-ethyl phosphate, mono-, di- and tri-isobutyl phosphate, mono-, di- and tri-butyl phosphate, mono-, di- and tri-lauryl phosphate, and phosphorous acids obtained by converting the phosphate moieties thereof into phosphites;

[0139] Organophosphorus compounds such as dialkyl dithiophosphoric acids represented by dimethyl dithiophosphoric acid;

[0140] Phenol, catechol, tert-butylcatechol, 2,6-di-tert-butylcresol, 2,6-di-tert-butylethylphenol, resorcinol, hydroquinone, phloroglucinol, pyrogallol, cresol, ethylphenol, butylphenol, nonylphenol, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, hydroxyphenylacetamide, methyl hydroxyphenylacetate, ethyl hydroxyphenylacetate, hydroxyphenylethanol, hydroxyphenylethylamine, hydroxybenzaldehyde, phenylphenol, bisphenol-A, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), bisphenol-F, bisphenol-S, α-naphthol, β-naphthol, aminophenol, chlorophenol, 2,4,6-trichlorophenol and other phenols;

[0141] 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, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 4B acid, diaminostilbenesulfonic acid, biphenylsulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, perisulfonic acid, Laurentic acid, phenyl J acid and other sulfonic acids, etc.

[0142] 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 them, 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.

[0143] For the product solution after the reaction, by washing with an acidic aqueous solution, the stability over time of the obtained compound (I) can be improved. As a specific example of the acid used in the acidic aqueous solution, the acid exemplified as a polymerization inhibitor in the above text can be cited. The acid can be used alone or in combination with two or more. There is a tendency that the acidic aqueous solution usually shows an effect below pH 6, but the more effective range is below pH 3. 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.

[0144] In addition, in order to improve the stability of compound (I), a hydrogen sulfide adsorbent may also be used. Examples of the hydrogen sulfide adsorbent include iron (III) hydroxide, zinc oxide, KNK-301 (zinc oxide adsorbent, manufactured by Kureha Oil & Fats Industries Co., Ltd.), NIONON 202A (iron oxide adsorbent, manufactured by Ibuki Masa Co., Ltd.), and LIMONIC (iron hydroxide, manufactured by Japan Limonite Co., Ltd.). The hydrogen sulfide adsorbent may be added during the reaction or used in the purification after the reaction.

[0145] From the viewpoint of easily and fully obtaining the effects of the present invention, the content of the component (A) may be, for example, 30 to 99% by mass based on the total amount of the solid content of the composition. The content of the component (A) is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and preferably 97% by mass or less, more preferably 95% by mass or less, and further preferably 92% by mass or less, based on the total amount of the composition.

[0146] The total amount of the solid content of the composition refers to the total amount of the components contained in the composition except the solvent. The content of each component in the solid content of the composition can be measured by known analytical methods such as liquid chromatography and gas chromatography. The content of each component in the solid content of the composition can also be calculated based on the formulation when the composition is prepared.

[0147] (B) Component: Compound (Z)

[0148] The composition of this embodiment contains the component (B). The component (B) is a naphthalene compound having an iodine atom. Since the composition contains the component (B), a cured product having a higher refractive index can be provided.

[0149]

[0150] In formula (Z),

[0151] R i represents a monovalent substituent, R i There are multiple cases where there are multiple Ri Can be the same or different.

[0152] p represents an arbitrary integer from 1 to 8.

[0153] q represents an arbitrary integer from 0 to 7.

[0154] The sum of p and q is less than 8.

[0155] R i The monovalent substituent represented by R can be exemplified by 2 The monovalent substituent represented by is the same substituent as that represented by .

[0156] p represents any integer of 1 to 8. p is preferably any integer of 1 to 3, and more preferably 1 or 2.

[0157] 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.

[0158] From the viewpoint of easily and fully obtaining the effects of the present invention, the content of the component (B) may be, for example, 1 to 70% by mass based on the total amount of the solid content of the composition. The content of the component (B) is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, based on the total amount of the composition.

[0159] Component (C): Polymerization initiator

[0160] The composition may contain one or more (C) components. As the (C) component, there is no particular limitation as long as it can initiate the polymerization of the (A) component, and for example, free radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, free radicals and cationic polymerization initiators, etc. can be cited. The free radical polymerization initiator, cationic polymerization initiator, or anionic polymerization initiator utilizes at least one of active energy ray irradiation and heat to generate free radicals, acids, or bases, respectively, so that the free radical polymerization, cationic polymerization, or anionic polymerization of the (A) component can be carried out. It should be noted that the (A) component can also be polymerized and cured by at least one of active energy ray irradiation and heat in the absence of a polymerization initiator.

[0161] 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. Examples of photoradical polymerization initiators that initiate radical polymerization by irradiation with active energy rays include oxime compounds, alkylphenone compounds, arylketone compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds.

[0162] Cationic polymerization initiators are compounds that can release substances that initiate 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. Depending on the difference in structure, they can initiate cationic polymerization by at least one of active energy ray irradiation and heat. Compounds that can release substances that initiate cationic polymerization by active energy ray irradiation are called photocationic polymerization initiators, and compounds that can release substances that initiate cationic polymerization by heat are called thermal cationic polymerization initiators.

[0163] Anionic polymerization initiators are compounds that can release substances that initiate anionic polymerization by at least one of active energy ray irradiation and heat. As anionic polymerization initiators, ammonium salts, DBU (diazabicycloundecenium) salts, DBN (diazabicyclononenium) salts, biguanidium salts, aromatic phosphonium salts, aromatic dimethyl urea, aliphatic dimethyl urea, etc. can be cited. They can initiate anionic polymerization by at least one of active energy ray irradiation and heat according to their structural differences. Compounds that can release substances that initiate anionic polymerization by active energy ray irradiation are called photoanionic polymerization initiators, and compounds that can release substances that initiate anionic polymerization by heat are called thermal anionic polymerization initiators.

[0164] When the composition contains the component (C), from the viewpoint of improving the heat resistance of the composition and its cured product, the composition preferably contains a thermal cationic polymerization initiator or a thermal anionic polymerization initiator, and more preferably contains a thermal anionic polymerization initiator.

[0165] When the composition contains component (C), the content of the polymerization initiator is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the total amount of component (A) and curable compounds other than component (A), from the viewpoint of improving curability and / or heat resistance, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, from the viewpoint of improving the physical properties such as mechanical properties of the cured product.

[0166] (D) Component: Polymerization Inhibitor

[0167] The composition may contain one or more (D) components. Whether to include a polymerization inhibitor in the composition is preferably determined by considering, for example, the type of (C) component. (C) component is preferably a component that is dissolved or dispersed in a solvent. The (D) component contained in the composition may be a component added when preparing the composition, or may be a component added after manufacturing the (A) component. By including the (D) component in the composition, the undesired polymerization of the (A) component can be suppressed, thereby improving the storage stability of the composition.

[0168] Examples of the component (D) include the same components as the polymerization inhibitor added to the reaction system to inhibit the polymerization of the generated compound (I). The component (D) is preferably formic acid or acetic acid.

[0169] When the composition contains component (D), the content of component (D) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.5 parts by mass or more, 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, further preferably 25 parts by mass or less, and particularly preferably 10 parts by mass or less, relative to 100 parts by mass of the total amount of component (A), from the viewpoint of improving the storage stability of the composition.

[0170] Examples of other components included in the composition include resins, curable compounds other than component (A), solvents, additives, etc. Examples of additives include inorganic particles, fillers, polymerization initiation aids, sensitizers, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, ultraviolet absorbers, antioxidants, dispersants, etc.

[0171] (resin)

[0172] The composition may contain one or more resins. By making the composition contain a resin, it is possible to impart developability to the cured product of the composition, or to adjust the mechanical properties and / or optical properties of the cured product and a molded product containing the same. As the resin, for example, thermoplastic resins and curable resins can be cited. 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.

[0173] As thermoplastic resins, for example, olefin resins such as polyethylene resins, polypropylene resins, and polycycloolefin resins; (meth) acrylic resins such as poly(meth) acrylate resins; styrene resins such as polystyrene resins, styrene-acrylonitrile resins, and acrylonitrile-butadiene-styrene resins; vinyl resins such as polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, polyvinyl butyral resins, ethylene-vinyl acetate copolymers, and ethylene-vinyl alcohol resins; polyester resins such as polyethylene terephthalate resins, polybutylene terephthalate resins, and liquid crystal polyester resins; polyacetal resins; polyamide resins; polycarbonate resins; polyurethane resins; polyphenylene sulfide resins, etc. One or more of these resins may be used as a polymer blend or polymer alloy.

[0174] Examples of the curable resin include resins having a photopolymerizable group or a thermally polymerizable group, and more specifically, include (meth)acrylic resins, epoxy resins, melamine resins, unsaturated polyester resins, phenolic resins, urea resins, alkyd resins, polyimide resins, and the like.

[0175] As other examples of resins, alkali-soluble resins can be mentioned. By making the composition contain alkali-soluble resins, it is possible to impart developability to the cured product of the composition. The so-called alkali-soluble resin refers to a resin that is soluble in an alkaline aqueous solution. Specifically, for example, a resin having a carboxyl group and / or a phenolic hydroxyl group can be mentioned.

[0176] 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 obtained, for example, by titrating with a potassium hydroxide aqueous solution.

[0177] In addition, as another example of the resin, there is a high refractive index resin. The high refractive index resin refers to a resin having a refractive index of 1.60 or more at a wavelength of 550 nm.

[0178] The weight average molecular weight (Mw) of the resin measured by gel permeation chromatography (GPC) in terms of standard polystyrene can be, for example, 5 to 2 million, preferably 1,000 to 1,000,000, 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 the raw materials used, the charging method, the reaction temperature, and the time.

[0179] When the composition contains a resin, the content of the resin 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 solid content of the composition.

[0180] (Curable compounds other than component (A) (compound (I)))

[0181] The composition may contain one or more curable compounds other than component (A). By making the composition contain curable compounds other than 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 the molded product containing the same can be adjusted.

[0182] Examples of the curable compound other than the component (A) include epithiol (thiirane) compounds other than the component (A), thietane compounds other than the component (A), epoxy compounds other than the component (A), oxetane compounds other than the component (A), hydroxy compounds, vinyl ether compounds, allyl compounds, thiol compounds, polyphenol compounds, iso(thio)cyanate compounds, (meth)acrylate compounds, and acid anhydrides.

[0183] When the composition contains a curable compound other than component (A), the content of the curable compound other than component (A) is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, based on the total amount of the solid content of the composition.

[0184] (Solvent)

[0185] The composition may contain one or more solvents. The solvent is preferably a solvent capable of dissolving or dispersing component (A), and more preferably a solvent capable of dissolving or dispersing other components other than component (A). As the solvent, for example, the solvent (organic solvent) exemplified in the reaction of compound (II) and compound (III) can be used.

[0186] 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, 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 the 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.

[0187] <Solidified and molded products>

[0188] The cured product of one embodiment is a cured product of a composition. The molded product of one embodiment is formed by curing the composition, and includes a cured product of the composition. The film-forming property, curing property, etc. of the composition are excellent, and therefore, it can be suitably used as a curable material for making a cured product or a molded product including it. The cured product can be obtained by curing the (A) component in the composition by utilizing at least one of the irradiation of active energy rays and heat. The shape of the molded product including the cured product is not particularly limited, and may include a film, a plate, a lens, a powder, a granular, a non-spherical particle, a broken particle, a porous, a blocky continuum, a fiber, a tubular, a hollow filament, etc., and may be any shape corresponding to the purpose of the molded product.

[0189] The method for obtaining a molded product from the composition is not particularly limited, and examples thereof include a method of forming a film on a substrate and then molding by etching or the like, an injection molding method, and a cast polymerization molding method.

[0190] In the cast polymerization molding method, for example, the composition is injected into a molding die, degassed as needed, and then cured by heating in an oven, etc., and the obtained molded product is taken out. The taken out molded product may be further irradiated with active energy rays for additional curing.

[0191] In the case of forming a film as a molding on a substrate, the composition can be applied to the substrate, dried as needed to form a coating film (coating layer), and the coating film (coating layer) is cured to obtain a molding as a cured film (cured layer). The molding can also be a patterned cured film (cured layer). The patterned cured film can be obtained by patterning using methods such as photolithography, inkjet, and printing. The patterning method can be, for example, photolithography. Photolithography is the following method: the composition is applied to a substrate, dried as needed to form a coating film (coating layer), the coating film (coating layer) is exposed across a photomask, and the coating film (coating layer) after exposure is developed.

[0192] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass coated with silicon dioxide, and alkali-free glass; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; and substrates formed with thin films of aluminum, silver, or silver / copper / palladium alloys on these substrates. Examples of a method for applying the composition to the substrate include spin coating, slit coating, and slit and spin coating.

[0193] The light source used in the exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, a bandpass filter can be used to selectively extract light near 436 nm, near 408 nm, or near 365 nm from light with wavelengths in these ranges according to the absorption wavelength of the photopolymerization initiator. Specific examples of light sources include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, etc. After the pattern is exposed, the exposed coating film (coating layer) can also be heated before development (baking before development).

[0194] As the developer used in the development, for example, an aqueous solution containing alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, solvents, etc. can be cited. As the solvent, for example, the solvent (organic solvent) exemplified in the reaction of compound (II) and compound (III) can be used. The developer may contain a surfactant. As the development method, a spin-on immersion method, an immersion method, a spray method, etc. can be cited. The patterned cured film (cured layer) obtained by the development may also be further heated (post-baked).

[0195] The cured product or the molded product comprising it is formed by the composition, and therefore, can show a high refractive index. In addition, their refractive index can be controlled to a desired refractive index by adjusting the composition of the composition, etc. The refractive index at a wavelength of 550nm of the cured product or the molded product comprising it can 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 at a wavelength of 550nm of the cured product or the molded product comprising it is, for example, 2.000 or less, or 1.900 or less.

[0196] The refractive index of a cured product or a molded product containing the same at a wavelength of 550nm 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 formed with a cured film. Next, for the substrate formed with a cured film, a visible ultraviolet spectrophotometer (e.g., JASCO Corporation, "ISV-922") with an integrating sphere unit (e.g., JASCO Corporation, "V-650") is used to measure the transmission spectrum and reflection spectrum at a wavelength of 300nm to 800nm. Next, according to the transmission spectrum and the increase and decrease caused by the interference of the reflection spectrum from the reflection spectrum, the value of the wavelength of 550nm in the real reflection spectrum obtained by subtracting and smoothing, and the refractive index of the substrate, the refractive index of the cured product or the molded product containing the same at a wavelength of 550nm is calculated based on the Fresnel formula (e.g., Hecht Optics I Original 5th Edition, Maruzen Publishing, 2018, p.209-226). Thereby, the refractive index of the cured product or the molded product including the cured product at a wavelength of 550 nm can be obtained.

[0197] <Purpose of use>

[0198] As for the use of the cured product or molded product, for example, there can be mentioned glass substitutes and surface coating materials thereof; coating materials for window glass, lighting glass and light source protection glass of houses, facilities, transportation equipment, etc.; window films of houses, facilities, transportation equipment, etc.; interior and exterior decoration materials of houses, facilities, transportation equipment, etc. and interior and exterior decoration coatings and coating films formed by using the coatings; alkyd resin spray paints and coating films formed by using the coatings; acrylic spray paints and coating films formed by using the coatings; components for light sources emitting ultraviolet rays such as fluorescent lamps and mercury lamps; materials for blocking electromagnetic waves generated from precision machinery, components for electronic and electrical equipment, and various displays; containers or packaging materials for food, chemicals, medicines, etc.; sheets or films for bottles, boxes, blisters, cups, special packaging, laser disc coatings, and agricultural industries; anti-fading agents for printed materials, dyed materials, dyes and pigments, etc.; protective films for polymer supports (for example, plastic parts of machinery and automobile parts); printed material protective layers; inkjet media coatings; laminated matte materials; optical light sheets (optical light sheets); film); safety glass / windshield interlayer; electrochromic / photochromic applications; overlaminate film; solar heat control film; cosmetics such as sunscreen, shampoo, hair dye (rinse), and hair treatment; fiber products and fibers for clothing such as sportswear, stockings, and hats; home interior decorations 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 (for example, 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; signboards, markers, etc. and their surface coating materials; substrates used in optical devices, etc.; optical waveguides; holograms; LED sealing materials, etc.

[0199] The molded article can be suitably used as an optical product, i.e., a lens, used in an optical device. Examples of optical devices include solid-state imaging devices and display devices. In solid-state imaging devices, lenses for the purpose of improving the efficiency of focusing light into each photoelectric conversion element can be used. In addition, in display devices, lenses for the purpose of improving the efficiency of extracting light from pixels can be used. The lens can be a microlens. Examples of display devices include liquid crystal display devices and organic EL display devices.

[0200] As high refractive index materials, inorganic compounds such as zirconium oxide and titanium oxide are known in the past. However, when making a molded object containing a high refractive index material formed by an inorganic compound, it is sometimes difficult to perform etching and the molding is not easy. In addition, the high refractive index material sometimes scatters during molding and causes pollution problems. Such problems can be solved by using the high refractive index material of this embodiment as an organic compound.

[0201] The cured product of the composition of the present embodiment can be suitably used as a main chain cut-off type positive resist. In the formation of the resist pattern using the cured product of the composition of the present embodiment, by irradiation of ionizing radiation, etc. (for example, electron beams, KrF lasers, ArF lasers, EUV lasers, etc.), the main chain of the polymer of the (A) component constituting the cured product is cut off in the irradiated portion of the resist film, and low molecular weight occurs. Therefore, in the exposed part and the unexposed part, the solubility in the developer is different, forming a resist pattern. The resist pattern using the cured product of the composition of the present embodiment can be applied when forming a resist pattern in the manufacture of printed substrates such as build-up substrates; semiconductors; photomasks; molds, etc.

[0202] Example

[0203] Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. It should be noted that, unless otherwise specified, "parts" refer to "parts by mass".

[0204] [Synthesis example 1]

[0205] <Synthesis of Compound (I-1)>

[0206] Synthesis of Compound (I-A1)

[0207]

[0208] A four-necked flask equipped with a Dimroth condenser and a thermometer was placed in 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. Next, 15 parts of sodium hydroxide, 66 parts of acetone, and 203 parts of pure water were added to another flask, and after being completely dissolved, they were added dropwise to the four-necked flask over 1 hour. After the 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)).

[0209] conduct 1 H-NMR analysis and LC-MS measurement confirmed the formation of compound (I-A1).

[0210] 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)

[0211] LC-MS: [M+H] + =305.5

[0212] Synthesis of Compound (I-1)

[0213]

[0214] A four-necked flask equipped with a Dimroth condenser and a thermometer was placed in a nitrogen atmosphere, 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)).

[0215] conduct 1 H-NMR analysis and LC-MS measurement confirmed the formation of compound (I-1).

[0216] 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)

[0217] LC-MS: [M+H] + =337.5

[0218] [Examples 1 to 6, Comparative Examples 1 to 4, and Reference Examples 1 and 2]

[0219] <Preparation of Composition>

[0220] The ingredients shown in Table 1 were charged into 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 visually observed, and it was confirmed that the ingredients were uniformly dissolved. The compositions of Comparative Examples 2, 4, and 5 were turbid when visually observed, and it was confirmed that the ingredients were not uniformly dissolved.

[0221] The details of the abbreviations of the blending components shown in Table 1 are as follows.

[0222] (A) Ingredients: Sulfur-containing heterocyclic compounds

[0223] (A-1): Compound (I-1) synthesized in Synthesis Example 1

[0224] (B) Component: Compound (Z)

[0225] (B-1): A compound represented by formula (B-1)

[0226]

[0227] Component (C): Polymerization initiator

[0228] (C-1): DBN (diazabicyclononenium) salt type thermal anionic polymerization initiator (manufactured by San-Apro Co., Ltd., "U-CAT 1102")

[0229] (C-2): Ammonium salt type thermal cationic polymerization initiator (manufactured by KING INDUST RIES INC., "CXC-1821")

[0230] Curable compounds other than component (A)

[0231] Compound (Y1): a compound represented by the formula (Y1) (1,6-bis(glycidyloxy)naphthalene, manufactured by DIC Corporation, “EPICLON HP-4032D”)

[0232]

[0233] Compound (Y2): a compound represented by the formula (Y2) (bisphenol A diglycidyl ether, manufactured by DIC Corporation, "EPICLON EXA-850CRP")

[0234]

[0235] Compound (Y3): a compound represented by the formula (Y3) (2,2'-diglycidyloxy-1,1'-binaphthyl, SUGAI CHEMICAL INDUSTRY CO., LTD., "DGOBINL")

[0236]

[0237] Compound (Y4): a compound represented by the formula (Y4) (9-vinylcarbazole, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0238]

[0239] Solvents

[0240] Solvent (E-1): Cyclopentanone

[0241] It should be noted that the compound represented by formula (B-1) was synthesized with reference to J. Phys. Chem. A 2003, 107, 480-484.

[0242] <Evaluation Test>

[0243] (1) Film-forming properties

[0244] For the compositions of Examples 1 to 6, Comparative Examples 1 to 4, and Reference Examples 1 and 2, a coating film was formed by the following method, and the film-forming property was evaluated. About 3 mL of the composition was dropped onto an alkali-free glass plate (thickness 0.7 mm, Corning, "Eagle XG"), and spin-coated at 1000 rpm and 20 seconds using a spin coater (MIKASA, "MS-B100") to form a coating film. The alkali-free glass plate with the coating film formed was heated at 60°C for 2 minutes to remove the solvent.

[0245] 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. It should be noted that the so-called open hole defect refers to a state in which a hole with a diameter of 1 mm or more is opened on the coating film and the alkali-free glass plate is exposed. If the result is A, it can be said that the film-forming property is good.

[0246] A: Colorless and transparent, neither open hole defects nor white turbidity can be observed

[0247] D1: There is an open hole defect.

[0248] D2: leucorrhea.

[0249] Hereinafter, the compositions of Examples 1 to 6, Comparative Examples 1 and 2, and Reference Examples 1 and 2, which were evaluated as "A" and "D1" in (1), were evaluated.

[0250] (2) Formation of cured film

[0251] About 3 mL of the composition of Examples 1 to 6, Comparative Examples 1 and 2, and Reference Examples 1 and 2 were respectively dripped onto an alkali-free glass plate (thickness 0.7 mm, manufactured by Corning, “Eagle XG”), and spin-coated using a spin coater (manufactured by MIKASA Co., Ltd., “MS-B100”) at 1000 rpm and 20 seconds to form a coating film. The alkali-free glass plate with the coating film formed thereon was heated at 60°C for 2 minutes to remove the solvent. Next, the alkali-free glass plate with the coating film formed thereon was heated at 120°C for 10 minutes as a post-bake to obtain an alkali-free glass with a cured film formed thereon. The film thickness of the cured film on the alkali-free glass was measured using a stylus film thickness meter (manufactured by Bruker, “DekTak XT”), and the result was that the film thickness was 1.5 μm.

[0252] (3) Determination of refractive index

[0253] For the alkali-free glass formed with a cured film produced in (2) above, a visible ultraviolet spectrophotometer (made by JASCO Corporation, "V-650") with an integrating sphere unit (made by JASCO Corporation, "ISV-922") was used to measure the transmission spectrum and reflection spectrum at wavelengths of 300nm to 800nm. Based on the value of the wavelength of 550nm in the true reflection spectrum obtained by subtracting the increase and decrease caused by the interference of the reflection spectrum from the transmission spectrum and the reflection spectrum and smoothing, and the refractive index of the alkali-free glass plate (made by Corning, "Eagle XG"), the refractive index of the cured film at a wavelength of 550nm was calculated based on the Fresnel formula (Hecht Optics I Original Works 5th Edition, Maruzen Publishing, 2018, p.209-226). The results are shown in Table 1.

[0254] [Table 1]

[0255]

[0256] As shown in Table 1, the composition of the example is superior in film-forming property and refractive index compared with the composition of the comparative example. From these results, it was confirmed that the composition of the present invention can provide a cured product having a high refractive index without impairing film-forming property.

Claims

1. A composition comprising: (A) a compound having at least one thiirane group or thietanyl group; and (B) a compound represented by formula (Z), In formula (Z), R i represents a monovalent substituent, R i There are multiple cases where there are multiple R i It can be the same or different; p represents any integer from 1 to 8; q represents any integer from 0 to 7; in, The sum of p and q is less than 8.

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

3. The composition according to 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 thietanyl group is a compound represented by formula (I), In formula (I), L represents a single bond or a divalent group, and two Ls may be the same or different; A 1 Represents oxygen or sulfur atoms, with two A 1 Can be the same or different; among them, there are two A 1 At least one of is a sulfur atom; m represents 0 or 1, and there are two m that can be the same or different; n represents any integer from 0 to 6; R 1 represents a monovalent substituent, R 1 There are multiple cases where there are multiple R 1 It can be the same or different; R 2 represents a hydrogen atom or a monovalent substituent, and there are two R 2 Can be the same or different.

5. A molded article formed 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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