Composition and its cured products, molded products, sheet-like molded products, and optical waveguides

Abstract

Providing a composition capable of giving a cured product having a high refractive index and excellent yellowing resistance. 【Solution means】There is provided a composition containing a compound (A) represented by formula (II) and a compound (B) represented by formula (B). JPEG2026108589000038.jpg27149 [In formula (II), A 1x represents an oxygen atom or a sulfur atom. However, at least one is a sulfur atom. mx represents 0 or 1. nx represents an integer of any one of 0 to 6.] JPEG2026108589000039.jpg21149 [In formula (B), R b1 , R b2 , R b3 , and R b4 each independently represents a monovalent hydrocarbon group. X - represents a halide ion.]

Description

[Technical Field]

[0001] The present invention relates to compositions and their cured products, molded articles, sheet-like molded articles, and optical waveguides. [Background technology]

[0002] Optical waveguides are structures designed to transmit light along a specific path and play a crucial role in various optical devices such as optical fibers and integrated optical circuits. Typically, optical waveguides consist of a core formed from a high refractive index core material and a cladding made from a low refractive index cladding material surrounding the core. This structure allows light to be transmitted through the core to its destination without leakage.

[0003] High refractive index materials are desired for core materials used to form cores. Conventionally, compositions containing episulfide compounds (compounds having a thiirane group) are known as such high refractive index materials (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2011 / 105014 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, cured products obtained from conventional episulfide compounds (compounds containing a thiirane group) do not have a sufficient refractive index when used as core materials, and further improvements in refractive index are required. In addition, cured products obtained from these compositions may undergo yellowing (color degradation), and improvements in these areas are also desired.

[0006] Therefore, the main object of the present invention is to provide a composition capable of providing a cured product that exhibits a high refractive index and is excellent in yellowing resistance.

Means for Solving the Problems

[0007] The present invention provides the composition described in [1] to [3], the cured product described in [4], the sheet-shaped molded product described in [5], and the optical waveguide described in [6]. [1] A compound (A) represented by formula (II), A compound (B) represented by formula (B), and a composition containing the same.

Chemical Formula

[0008] The present invention provides a composition capable of producing a cured product that exhibits a high refractive index and excellent resistance to yellowing. Some forms of the composition tend to also exhibit superior haze in the cured product. Furthermore, the present invention provides a cured product of such a composition, a sheet-like molded product obtained by curing such a composition, and an optical waveguide including the sheet-like molded product. [Modes for carrying out the invention]

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

[0010] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages within this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples.

[0011] In this specification, (meth)acrylate means acrylate or the corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl group and (meth)acrylic acid ester.

[0012] In this specification, unless otherwise specified, the materials exemplified below may be used individually or in combination of two or more, to the extent that the conditions are met. The content of each component refers to the total amount of multiple substances corresponding to each component, unless otherwise specified.

[0013] <Composition> The composition of one embodiment contains compound (A) represented by formula (II) (hereinafter sometimes referred to as "component (A)") and compound (B) represented by formula (B) (hereinafter sometimes referred to as "component (B)"). According to the composition of this embodiment, it is possible to provide a cured product that exhibits a high refractive index and has excellent resistance to yellowing.

[0014] (A) Component: Compound represented by formula (II) The composition of this embodiment contains component (A). Component (A) may be a curable compound. By containing component (A) in the composition, component (A) itself can polymerize to produce a cured product exhibiting a high refractive index.

[0015] [ka]

[0016] In formula (II), L 1x represents a single bond or a divalent group, and there are two L 1x They may be the same or different. A 1x represents an oxygen atom or a sulfur atom, and there are two A 1x They may be the same or different. However, if there are two A 1x At least one of them is a sulfur atom. mx represents either 0 or 1, and the two mx values ​​may be the same or different. nx represents an integer between 0 and 6. R 1x represents a monovalent substituent, R 1x If there are multiple R 1x They may be the same or different. R 2x R represents a hydrogen atom or a monovalent substituent, and there are two R 2x They may be the same or different.

[0017] In the compound represented by formula (II), the two groups represented by formula (II-c) may be bonded to any position between positions 1 and 8 of the naphthalene ring. The group represented by formula (II-c) on the naphthalene ring may be bonded to any two positions between positions 1 and 4 (or between positions 5 and 8), or to any one position between positions 1 and 4 (or between positions 5 and 8) and any one position between positions 5 and 8 (or between positions 1 and 4). Preferably, the group represented by formula (II-c) on the naphthalene ring is bonded to any one position between positions 1 and 4 (or between positions 5 and 8) and any one position between positions 5 and 8 (or between positions 1 and 4).

[0018] [ka]

[0019] In formula (II-c), L 1x , A 1x , mx, and R 2x The above has the same meaning as above, and * indicates the joining position.

[0020] R contains one or more compounds represented by formula (II). 1x If it has a monovalent substituent represented by R 1x The monovalent substituent represented by may be bonded to any position from 1 to 8 on the naphthalene ring, excluding the bonded position of the group represented by formula (II-c).

[0021] L 1x represents a single bond or a divalent group, and there are two L1x They may be the same or different. In the compound represented by formula (II), there are two L 1x Preferably, at least one of the groups is an alkanediyl group, and more preferably, both are alkanediyl groups. In this case, the number of carbon atoms in the alkanediyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.

[0022] L 1x Examples of divalent groups represented by include divalent aliphatic chain hydrocarbon groups which may have substituents; divalent alicyclic hydrocarbon groups which may have substituents; divalent aromatic hydrocarbon groups which may have substituents; and divalent groups which are combinations of these (e.g., aralkylene groups). The methylene group (-CH2-) included in the divalent group is -O-, -S-, -NR A -(R A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It may be substituted with -CO- or -SO2-.

[0023] Examples of divalent aliphatic chain hydrocarbon groups include saturated or unsaturated aliphatic chain hydrocarbon groups. More specifically, examples include methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl group, octanediyl group, nonanediyl group, decanediyl group, undecanediyl group, dodecanediyl group, tridecanediyl group, tetradecanediyl group, pentadecanediyl group, hexadecanediyl group, heptadecanediyl group, octadecanediyl group, nonadecanediyl group, eicosanediyl group, and other alkanediyl groups. Divalent aliphatic chain hydrocarbon groups may be linear or branched. The number of carbon atoms in a divalent aliphatic chain hydrocarbon group is usually 1 to 20, preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.

[0024] Examples of substituents that a divalent aliphatic chain hydrocarbon group may have include halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxyl groups; amino groups; acetyl groups; and cyano groups.

[0025] Examples of divalent alicyclic hydrocarbon groups include saturated or unsaturated alicyclic hydrocarbon groups. More specifically, monocyclic alicyclic hydrocarbon groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cyclooctanediyl, cyclononanediyl, and cyclodecanediyl groups; and polycyclic alicyclic hydrocarbon groups such as bicyclo[1.1.0]butanediyl, tricyclo[2.2.1.0]heptanediyl, bicyclo[3.2.1]octanediyl, bicyclo[2.2.2]octanediyl, adamantanediyl, bicyclo[4.3.2]undecanediyl, and tricyclo[5.3.1.1]dodecanediyl groups. The number of carbon atoms in a divalent alicyclic hydrocarbon group is usually 3 to 20, preferably 3 to 10, more preferably 3 to 6, and even more preferably 5 or 6.

[0026] Examples of substituents that a divalent alicyclic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; hydroxyl groups; amino groups; acetyl groups; and cyano groups.

[0027] The divalent aromatic hydrocarbon group may be monocyclic or polycyclic. Examples of divalent aromatic hydrocarbon groups include phenylene, naphthylene, anthracenediyl, and fluo-orangeyl groups. The number of carbon atoms in the divalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0028] Examples of substituents that a divalent aromatic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; hydroxyl groups; amino groups; acetyl groups; and cyano groups.

[0029] A 1x represents an oxygen atom or a sulfur atom, and there are two A 1x They may be the same or different. However, if there are two A 1x At least one of them is a sulfur atom. In the compound represented by formula (II), two A 1x Preferably, both are sulfur atoms. 1x As the number of sulfur atoms increases, it tends to be possible to obtain cured products that exhibit a higher refractive index and have better solvent resistance.

[0030] mx represents either 0 or 1, and the two mx values ​​may be the same or different. In the compound represented by formula (II), the two mx values ​​are preferably both 0.

[0031] nx represents an integer from 0 to 6. Preferably, nx is an integer from 0 to 3, more preferably from 0 to 2, even more preferably 0 or 1, and particularly preferably 0.

[0032] R 1x represents a monovalent substituent, R 1x If there are multiple R 1x They may be the same or different.

[0033] R 1xExamples of monovalent substituents represented by include monovalent hydrocarbon groups such as optionally substituted monovalent aliphatic chain hydrocarbon groups, optionally substituted monovalent alicyclic hydrocarbon groups, optionally substituted monovalent aromatic hydrocarbon groups, and monovalent groups consisting of combinations thereof (e.g., aralkyl groups); hydroxyl groups; amino groups which may be substituted with one or two alkyl groups having 1 to 6 carbon atoms, such as amino groups, monomethylamino groups, monoethylamino groups, dimethylamino groups, diethylamino groups, and methylethylamino groups; and pyrrolidine groups. Examples include aliphatic heterocyclic groups with 4 to 20 carbon atoms such as nyl groups, pyrrolinyl groups, imidazolidinyl groups, imidazolinyl groups, oxazolinyl groups, thiazolyl groups, piperidinyl groups, morpholinyl groups, piperazinyl groups, indolyl groups, isoindolyl groups, quinolyl groups, thienyl groups, pyrrolyl groups, and furyl groups, or heterocyclic groups with 3 to 20 carbon atoms such as aromatic heterocyclic groups; halogen atoms; nitro groups; cyano groups; carboxyl groups; sulfo groups; thiol groups; formyl groups; -SF3 groups; -SF5 groups; ethenyl (vinyl) groups; ethynyl groups; and -SO3Na groups. Methylene groups (-CH2-) included in monovalent substituents are -O-, -S-, and -NR. B -(R B The ∫ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It may be substituted with -CO- or -SO2-. Examples of groups in which the methylene group (-CH2-) in a monovalent substituent is substituted with -O- include alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, and octyloxy groups; and alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, and methoxyethyl groups.

[0034] Examples of monovalent aliphatic hydrocarbon groups include saturated or unsaturated aliphatic hydrocarbon groups. More specifically, examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups. Monovalent aliphatic hydrocarbon groups may be linear or branched. The number of carbon atoms in a monovalent aliphatic hydrocarbon group is usually 1 to 20, preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, particularly preferably 1 to 4, and most preferably 1 or 2.

[0035] Examples of substituents that a monovalent aliphatic chain hydrocarbon group may have include halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxyl groups; amino groups; acetyl groups; cyano groups; and nitro groups.

[0036] Examples of monovalent alicyclic hydrocarbon groups include saturated or unsaturated alicyclic hydrocarbon groups. More specifically, monocyclic alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, and cyclodecyl groups; and polycyclic alicyclic hydrocarbon groups such as bicyclo[1.1.0]butyl, tricyclo[2.2.1.0]heptyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, adamantyl, bicyclo[4.3.2]undecyl, and tricyclo[5.3.1.1]dodecyl groups. The number of carbon atoms in a monovalent alicyclic hydrocarbon group is usually 3 to 20, preferably 3 to 10, more preferably 3 to 6, and even more preferably 5 or 6.

[0037] Examples of substituents that a monovalent alicyclic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; hydroxyl groups; amino groups; acetyl groups; cyano groups; and nitro groups.

[0038] The monovalent aromatic hydrocarbon group may be monocyclic or polycyclic. Examples of monovalent aromatic hydrocarbon groups include phenyl, naphthyl, anthracenyl, fluorenyl, and pyrenyl groups. The number of carbon atoms in the monovalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0039] Examples of substituents that a monovalent aromatic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms), such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; hydroxyl groups; amino groups; acetyl groups; cyano groups; and nitro groups.

[0040] R 2x R represents a hydrogen atom or a monovalent substituent, and there are two R 2x They may be the same or different. 2x As a monovalent substituent represented by , R 1x Examples of monovalent substituents similar to those represented by formula (II) can be given. In the compound represented by formula (II), there are two R 2x Preferably, it is a hydrogen atom or a monovalent aliphatic chain hydrocarbon group, more preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group having 1 to 6 carbon atoms, even more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

[0041] (A) Examples of component (compound represented by formula (II)) include compounds represented by formula (II-A), formula (II-B), formula (II-C), formula (II-D), formula (II-E), and formula (II-F). L in formulas (II-A), (II-B), (II-C), (II-D), (II-E), and (II-F) 1x , A 1x ,mx,nx,R 1x , and R 2x This expresses the same meaning as above.

[0042] [ka]

[0043] In equations (II-A), (II-B), (II-C), (II-D), (II-E), and (II-F), there are two L 1x Preferably, at least one of the groups is an alkanediyl group, and more preferably, both are alkanediyl groups. In this case, the number of carbon atoms in the alkanediyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2.

[0044] In formulas (II-A), (II-B), (II-C), (II-D), (II-E), and (II-F), the two mx values ​​are each independently 0 or 1, preferably 0.

[0045] In equations (II-A), (II-B), (II-C), (II-D), (II-E), and (II-F), nx is independently an integer from 0 to 6, preferably an integer from 0 to 3, more preferably an integer from 0 to 2, even more preferably 0 or 1, and particularly preferably 0.

[0046] In equations (II-A), (II-B), (II-C), (II-D), (II-E), and (II-F), there are two A 1x Each of these is independently either an oxygen atom or a sulfur atom. However, there are two A 1x At least one of them is a sulfur atom. 1x Preferably, both are sulfur atoms.

[0047] In equations (II-A), (II-B), (II-C), (II-D), (II-E), and (II-F), there are two R 2x Each of these is independently preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group, more preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group having 1 to 6 carbon atoms, even more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group. 2x They are preferably the same.

[0048] The following are specific examples of component (A) (compounds represented by formula (II)), but are not limited to these.

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064] [ka]

[0065] The molecular weight of component (A) (the compound represented by formula (II)) is preferably 2000 or less, more preferably 1000 or less, and even more preferably 750 or less, from the viewpoint of synthesis. The molecular weight of component (A) is preferably 50 or more, more preferably 100 or more, and even more preferably 150 or more, from the viewpoint of volatility.

[0066] (A) The compound represented by formula (II) as a component can be obtained by synthesizing the compound represented by formula (II-1) and reacting the compound represented by formula (II-1) with a sulfidating agent.

[0067] [ka]

[0068] In formula (II-1), L 1x ,mx,nx,R 1x , and R 2x This has the same meaning as (Equation (II)) above.

[0069] The compound represented by formula (II-1) can be obtained, for example, by a method that includes a step of reacting the compound represented by formula (II-1a) with the compound represented by formula (II-1b).

[0070] [ka]

[0071] In equation (II-1a), nx and R 1x This expresses the same meaning as above.

[0072] [ka]

[0073] In formula (II-1b), L1x , mx, and R 2x This has the same meaning as above, X 1x represents a leaving group.

[0074] The reaction between the compound represented by formula (II-1a) and the compound represented by formula (II-1b) can be carried out, for example, in the presence of a base. Examples of bases include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium hydride, lithium aluminum hydride, sodium borohydride, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, and cesium bicarbonate; metal alkoxides such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium t-butoxide, and potassium t-butoxide; and organic bases such as ammonia, methylamine, dimethylamine, trimethylamine, triethylamine, diisopropylethylamine, triisopropylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), pyridine, 2,6-dimethylpyridine, 2,6-di-t-butylpyridine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, and tetramethylammonium chloride. The amount of base used may be, for example, 0.0001 to 10 moles per mole of the compound represented by formula (II-1a), preferably 0.001 to 5 moles, more preferably 0.01 to 4 moles, and even more preferably 0.1 to 3 moles.

[0075] Furthermore, two or more bases may be used in combination. When used in combination, it is preferable to use a combination of a carbonate such as sodium carbonate, potassium carbonate, lithium carbonate, or cesium carbonate, or a bicarbonate such as sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, or cesium bicarbonate, and a metal hydroxide such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or cesium hydroxide, or a metal alkoxide such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium t-butoxide, or potassium t-butoxide, and it is more preferable to use a combination of a bicarbonate and a metal hydroxide. When used in combination, the two types may be added simultaneously or in stages.

[0076] In the compound represented by formula (II-1b), X 1x Examples of leaving groups represented by formula (II-1b) include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, trifluoromethylsulfonyl, perfluoroethylsulfonyl, perfluoropropylsulfonyl, and perfluorobutylsulfonyl; and arylsulfonyl groups such as phenylsulfonyl, p-toluenesulfonyl, p-fluorophenylsulfonyl, and pentafluorophenylsulfonyl. Specific examples of compounds represented by formula (II-1b) include epihalohydrin compounds (L 1x It is a methylene group, and mx is 0, R 2x X is a hydrogen atom, 1x Examples include compounds in which (the compound is a halogen atom). The amount of compound represented by formula (II-1b) used may be, for example, 0.01 to 20 moles, preferably 0.5 to 15 moles, per mole of the compound represented by formula (II-1a). In this step, the reaction may be carried out using two or more compounds represented by formula (II-1b).

[0077] The reaction between the compound represented by formula (II-1a) and the compound represented by formula (II-1b) is preferably carried out in a solvent. Examples of solvents include water, ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, alcohols, glimes, esters, aliphatic nitriles, sulfoxides, and amides. The following are examples of solvents:

[0078] Ketones: Acetone, methyl ethyl ketone, diethyl ketone, butyl methyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, 2-octanone, cyclopentanone, cyclohexanone, etc. Aromatic hydrocarbons: benzene, toluene, xylene, mesitylene, naphthalene, anisole, nitrobenzene, aniline, tetralin, durene, etc. Halogenated aromatic hydrocarbons: Chlorobenzene, dichlorobenzene, chloronaphthalene, etc. Aliphatic hydrocarbons: pentane, hexane, heptane, etc. Aliphatic halogenated hydrocarbons: dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, tetrachloroethylene, etc. Ethers: Diethyl ether, diisopropyl ether, methyl t-butyl ether, cyclopentyl methyl ether, diphenyl ether, dimethoxyethane, dioxane, etc. Alcohols: methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, hexafluoroisopropanol, etc. Glymes: Methyl diglyme, ethyl diglyme, triglyme, diethylene glycol butyl methyl ether, etc. Esters: Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc. Aliphatic nitriles: Acetonitrile, etc. Sulfoxides: Dimethyl sulfoxide, sulfolane, etc. Amides: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0079] The reaction temperature between the compound represented by formula (II-1a) and the compound represented by formula (II-1b) may be, for example, -80 to 200°C, preferably -40 to 150°C, more preferably -20 to 120°C, and even more preferably -5 to 100°C.

[0080] In this way, the compound represented by formula (II-1) can be obtained. When the obtained compound represented by formula (II-1) is used in the synthesis of the compound represented by formula (II), the compound represented by formula (II-1) may be used after isolation, or it may be used as is without isolation.

[0081] The compound represented by formula (II) can be obtained, for example, by a method that includes a step of reacting the compound represented by formula (II-1) with a sulfurizing agent.

[0082] The reaction between the compound represented by formula (II-1) and a sulfurizing agent is a reaction in which the oxygen atom of the epoxy ring or oxetanyl ring of the compound represented by formula (II-1) is replaced with a sulfur atom using the sulfurizing agent, thereby forming a thiirane ring (episulfide ring) or thietane ring. Examples of sulfurizing agents include thiourea, methylthiourea, dimethylthiourea, trimethylthiourea, tetramethylthiourea, tetraethylthiourea, ethylenethiourea, phenylthiourea, diphenylthiourea, tolylthiourea, ditolylthiourea, sodium thiocyanate, potassium thiocyanate, etc. The amount of sulfurizing agent used can be arbitrarily adjusted according to the oxygen atom to be substituted. The amount of sulfurizing agent used is, for example, 0.01 to 20 moles, preferably 0.5 to 10 moles, per mole of the compound represented by formula (II-1). Furthermore, by adjusting the amount of sulfurizing agent used, the reaction temperature, the reaction time, etc., it is possible to replace both oxygen atoms in the compound represented by formula (II-1) with sulfur atoms, or to replace one of the oxygen atoms in the compound represented by formula (II-1) with a sulfur atom.

[0083] The reaction between the compound represented by formula (II-1) and the sulfiding agent is preferably carried out in a solvent. Examples of solvents include those similar to those exemplified in the reaction between the compound represented by formula (II-1a) and the compound represented by formula (II-1b). The reaction temperature between the compound represented by formula (II-1) and the sulfiding agent may be, for example, -80 to 200°C, preferably -40 to 100°C, more preferably -20 to 80°C, and even more preferably -5 to 60°C.

[0084] A polymerization inhibitor may be added to the reaction system to suppress the polymerization of the compound represented by formula (II) that is produced. Examples of polymerization inhibitors include acids and acid anhydrides. More specifically, Inorganic acidic compounds such as nitric acid, hydrogen chloride (hydrochloric acid), perchloric acid, hypochlorous acid, chlorine dioxide, hydrofluoric acid, sulfuric acid, fuming sulfuric acid, sulfuryl chloride, boric acid, arsenic acid, arsenous acid, pyroaric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphorus oxychloride, phosphorus oxybromide, phosphorus sulfide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, hydrogen cyanide, chromic acid, anhydrous nitric acid, anhydrous sulfuric acid, boron oxide, arsenic acid pentoxide, phosphorus pentoxide, anhydrous chromic acid, silica, alumina, aluminum chloride, zinc chloride, lithium hydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, cesium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, etc. Organic carboxylic acids such as formic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, propionic acid, butyric acid, succinic acid, valeric acid, caproic acid, caprylic acid, naphthenic acid, methyl mercaptopropionate, malonic acid, glutaric acid, adipic acid, cyclohexanecarboxylic acid, thiodipropionic acid, dithiodipropionic acid, maleic acid, benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, salicylic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, benzoylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, benzyl acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic acid anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, trifluoroacetic anhydride, and other organic carboxylic acids; Phosphates such as mono, di, and trimethyl phosphates, mono, di, and triethyl phosphates, mono, di, and triisobutyl phosphates, mono, di, and tributyl phosphates, mono, di, and trilauryl phosphates, and phosphites in which the phosphate portion thereof has been converted to a phosphite; Organophosphorus compounds such as dialkyldithiophosphates, exemplified by dimethyldithiophosphate; Phenols such as phenol, catechol, t-butylcatechol, 2,6-di-t-butylcresol, 2,6-di-t-butylethylphenol, resorcinol, hydroquinone, phloroglucin, pyrogallol, cresol, ethylphenol, butylphenol, nonylphenol, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, hydroxyphenylacetic acid amide, hydroxyphenylacetic acid methyl, hydroxyphenyl ethyl acetate, hydroxyphenethyl alcohol, hydroxyphenethylamine, hydroxybenzaldehyde, phenylphenol, bisphenol-A, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), bisphenol-F, bisphenol-S, α-naphthol, β-naphthol, aminophenol, chlorophenol, 2,4,6-trichlorophenol, and other phenols; Sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, p-toluenesulfonic acid, ethylbenzenesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid, p-phenolsulfonic acid, o-cresolsulfonic acid, metanylic acid, sulfanilic acid, 4B-acid, diaminostilbenesulfonic acid, biphenylsulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, peric acid, laurentic acid, phenylJ acid, etc. These are some examples.

[0085] The amount of polymerization inhibitor used may be, for example, 0.0001 to 1.0 mole per mole of the compound represented by formula (II), preferably 0.001 to 0.5 moles, more preferably 0.01 to 0.25 moles, and even more preferably 0.05 to 0.15 moles. Among these, the polymerization inhibitor is preferably acetic acid, acetic anhydride, maleic acid, maleic anhydride, phosphoric acid, alkali metal hydrogen phosphate, or alkali metal dihydrogen phosphate.

[0086] The long-term stability of the compound represented by formula (II) obtained by washing the reaction product solution with an acidic aqueous solution can be improved. Specific examples of acids used in the acidic aqueous solution include those exemplified above as polymerization inhibitors. These acids may be used alone or in mixtures of two or more. The acidic aqueous solution generally tends to exhibit its effect at pH 6 or below, but the most effective range is pH 3 or below. The acids used in the acidic aqueous solution are preferably aqueous solutions of hydrogen chloride (hydrochloric acid), sulfuric acid, phosphoric acid, and / or maleic acid.

[0087] Furthermore, hydrogen sulfide adsorbents can be used to improve the stability of the compound represented by formula (II). Examples of hydrogen sulfide adsorbents include iron(III) hydroxide, zinc oxide, KNK-301 (zinc oxide-based adsorbent, manufactured by Kureha Oil & Fat Industry Co., Ltd.), Nionon 202A (iron oxide-based adsorbent, manufactured by Ibuki Shoji Co., Ltd.), and Limonic (iron hydroxide-based, manufactured by Nippon Limonite Co., Ltd.). The hydrogen sulfide adsorbent may be added during the reaction or added during the purification process after the reaction.

[0088] The content of component (A) may be, for example, 30 to 99% by mass, based on the total amount of solids in the composition, in order to easily obtain the effects of the present invention. The content of component (A) is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, preferably 98.5% by mass or less, more preferably 98% by mass or less, and even more preferably 97.5% by mass or less, based on the total amount of solids in the composition.

[0089] The total amount of solids in a composition refers to the sum of the components contained in the composition, excluding the solvent. The content of each component in the solids of a composition can be measured using known analytical methods such as liquid chromatography and gas chromatography. The content of each component in the solids of a composition may also be calculated from the formulation at the time of composition preparation.

[0090] (B) Component: Compound (B) represented by formula (B) The composition of this embodiment contains component (B). Component (B) is a phosphonium salt. Component (B) is a component that acts as a curing agent for component (A). By containing component (B) in the composition, it becomes possible to provide a cured product having excellent yellowing resistance. Component (B) is preferably liquid at 20°C. When component (B) is liquid at 20°C, it becomes possible to advance the curing reaction of component (A) without using a solvent.

[0091]

Chemical formula

[0092] In formula (B), R b1 、R b2 、R b3 、and R b4 each independently represent a monovalent hydrocarbon group which may have a substituent. X - represents a halide ion.

[0093] Examples of the monovalent hydrocarbon group represented by R b1 、R b2 、R b3 、and R b4 are the same as those of the monovalent hydrocarbon group of the monovalent substituent represented by R 1x . The methylene group (-CH2-) contained in the monovalent hydrocarbon group may be substituted with -O-, -S-, -NR C -(R C represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.), -CO-, or -SO2-.

[0094] R b1 、R b2 、R b3 、and R b4The monovalent hydrocarbon group represented by is preferably an alkyl group having 1 to 16 carbon atoms which may have a substituent, more preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and still more preferably an alkyl group having 1 to 8 carbon atoms which may have a substituent, from the viewpoints of internal transmittance and haze. Examples of the alkyl group include the same ones as those in the alkyl group in the monovalent aliphatic chain hydrocarbon group which may have a substituent in the monovalent substituent represented by 1x . The methylene group (-CH2-) contained in the alkyl group may be substituted with -O-, -S-, -NR 1x -(R C -(R C represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)), -CO-, or -SO2-.

[0095] R b1 , R b2 , R b3 and R b4 may be the same or different from each other.

[0096] Examples of the halide ion represented by X - include fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ), etc. X - is preferably chloride ion (Cl - ), bromide ion (Br - ), or iodide ion (I - ).

[0097] (B) Examples of components include triethylpentylphosphonium bromide (liquid at 20°C), triethyloctylphosphonium bromide (liquid at 20°C), tributylhexylphosphonium bromide (liquid at 20°C), tetrabutylphosphonium chloride (liquid at 20°C), tributyldodecylphosphonium chloride (liquid at 20°C), tributylhexadecylphosphonium chloride (liquid at 20°C), trihexyltetradecylphosphonium chloride (liquid at 20°C), and tetraethylphosphonium bromide (solid at 20°C). Examples include tetrabutylphosphonium bromide (solid at 20°C), tetraoctylphosphonium bromide (solid at 20°C), tributyloctylphosphonium bromide (solid at 20°C), tributyl(cyanomethyl)phosphonium chloride (solid at 20°C), tributyldodecylphosphonium bromide (solid at 20°C), tributylhexadecylphosphonium bromide (solid at 20°C), tributylmethylphosphonium iodide (solid at 20°C), and ethyltrioctylphosphonium bromide (solid at 20°C). Among these, component (B) is preferably at least one selected from the group consisting of triethylpentylphosphonium bromide (liquid at 20°C), triethyloctylphosphonium bromide (liquid at 20°C), tributylhexylphosphonium bromide (liquid at 20°C), tetrabutylphosphonium chloride (liquid at 20°C), tributyldodecylphosphonium chloride (liquid at 20°C), tributylhexadecylphosphonium chloride (liquid at 20°C), and trihexyltetradecylphosphonium chloride (liquid at 20°C).

[0098] The content of component (B) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and particularly 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, heat resistance, adhesion, and film-forming properties, and preferably 15 parts by mass or less, more preferably 12.5 parts by mass or less, even more preferably 10 parts by mass or less, and particularly preferably 7.5 parts by mass or less, from the viewpoint of improving the physical properties such as the mechanical properties of the cured product.

[0099] solvent The composition may contain one or more solvents. Preferably, the solvent can dissolve or disperse component (A), and more preferably, it can dissolve or disperse other components other than component (A). Examples of solvents include the solvents exemplified in the reaction between the compound represented by formula (II-1a) and the compound represented by formula (II-1b) (organic solvents), ester solvents (solvents containing -COO- in the molecule but not -O-), ether solvents (solvents containing -O- in the molecule but not -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule but not -COO-), alcohol solvents (solvents containing OH in the molecule but not -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxides, and the like.

[0100] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0101] As ether solvents, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, phenethole, methylanisole, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, ethylene glycol ethyl methyl ether, ethylene glycol methylpropyl ether, ethylene glycol butyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene Dipropyl glycol ether, propylene glycol dibutyl ether, propylene glycol ethyl methyl ether, propylene glycol methyl propyl ether, propylene glycol butyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol methyl propyl ether, diethylene glycol butyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, dipropylene glycol ethyl methyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, triethylene glycol ethyl methyl ether,Examples include triethylene glycol methyl propyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dipropyl ether, tripropylene glycol dibutyl ether, tripropylene glycol ethyl methyl ether, tripropylene glycol methyl propyl ether, tripropylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol ethyl methyl ether, tetraethylene glycol methyl propyl ether, and tetraethylene glycol butyl methyl ether.

[0102] Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethyl ester ester Examples include ethyl toxic-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0103] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0104] Examples of alcoholic solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0105] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0106] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0107] If the composition contains a solvent, the solvent content is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, preferably 1000 parts by mass or less, and more preferably 500 parts by mass or less, based on 100 parts by mass of the total solid content of the composition. If the composition contains a solvent, the solid content concentration of the composition is preferably 5 to 60% by mass, more preferably 10 to 50% by mass.

[0108] Other components included in the composition include, for example, resins, curable compounds other than component (A), and additives. Examples of additives include inorganic particles, fillers, polymerization initiators, sensitizers, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, UV absorbers, antioxidants, and dispersants.

[0109] The composition of this embodiment may contain one or more resins. By including resins in the composition, it is possible to impart developability to the cured product of the composition, or to adjust the mechanical and / or optical properties of the cured product and the molded product containing it. Examples of resins include thermoplastic resins and curable resins. The curable resin may be a photocurable resin that hardens by irradiation with active energy rays, or a thermosetting resin that hardens by heat.

[0110] Examples of thermoplastic resins include olefin resins such as polyethylene resin, polypropylene resin, and polycycloolefin resin; (meth)acrylic resins such as poly(meth)acrylic acid ester resins; styrene resins such as polystyrene resin, styrene-acrylonitrile resin, and acrylonitrile-butadiene-styrene resin; vinyl resins such as polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol resin; polyester resins such as polyethylene terephthalate resin, polybutylene terephthalate resin, and liquid crystal polyester resin; polyacetal resin; polyamide resin; polycarbonate resin; polyurethane resin; and polyphenylene sulfide resin. One or more of these resins may be used as a polymer blend or polymer alloy.

[0111] Examples of curable resins include resins having photopolymerizable groups or thermopolymerizable groups. More specifically, examples include (meth)acrylic resins, epoxy resins, melamine resins, unsaturated polyester resins, phenolic resins, urea resins, alkyd resins, and polyimide resins.

[0112] Other examples of resins include alkali-soluble resins. The inclusion of an alkali-soluble resin in a composition can impart developability to the cured product of the composition. An alkali-soluble resin is a resin that is soluble in an alkaline aqueous solution. Specifically, examples include resins having carboxyl groups and / or phenolic hydroxyl groups.

[0113] The acid value of the alkali-soluble resin is preferably 10 to 170 mg KOH / g, more preferably 20 to 150 mg KOH / g, and even more preferably 30 to 140 mg KOH / g, from the viewpoint of improving the developability and solvent resistance of the cured product of the composition. The acid value is measured as the amount of potassium hydroxide (mg) required to neutralize 1 g of alkali-soluble resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

[0114] Another example of a resin is a high refractive index resin. A high refractive index resin is a resin whose refractive index at a wavelength of 550 nm is 1.60 or higher.

[0115] The weight-average molecular weight (Mw) of the resin, measured by gel permeation chromatography (GPC) on a standard polystyrene basis, may be, for example, 5 to 2 million, preferably 10 to 1 million, and more preferably 15 to 750,000. The Mw of the resin can be adjusted by appropriately combining reaction conditions such as the selection of raw materials used, the preparation method, the reaction temperature, and the reaction time.

[0116] If the composition contains a resin, the resin content is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 80% by mass or less, and more preferably 70% by mass or less, based on the total amount of solids in the composition.

[0117] The composition of this embodiment may contain one or more curable compounds other than component (A). By including curable compounds other than component (A) in the composition, the viscosity or curability of the composition can be adjusted, and the mechanical and / or optical properties of the resulting cured product and the molded product containing it can be adjusted.

[0118] Examples of curable compounds other than component (A) include epoxy compounds other than component (A), oxetane compounds other than component (A), hydroxy compounds, vinyl ether compounds, allyl compounds, thiol compounds, polyphenol compounds, iso(thio)cyanate compounds, acid anhydrides, and the like.

[0119] If the composition contains curable compounds other than component (A), the content of curable compounds other than component (A) is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 30% by mass or less, and more preferably 20% by mass or less, based on the total amount of solids in the composition.

[0120] The composition can be suitably used in the manufacture of optical waveguides (particularly the core of an optical waveguide).

[0121] <Cured products and molded products> The cured product of one embodiment is a cured product of the composition. The molded product of one embodiment is obtained by curing the composition and includes the cured product of the composition. The composition has excellent storage stability, resistance to yellowing, and curability on acidic surfaces, and can therefore be suitably used as a curable material for producing a cured product or a molded product containing it. The cured product can preferably be obtained by curing component (A) in the composition by heat. The shape of the molded product containing the cured product is not particularly limited and may include film-like, sheet-like (or plate-like), lens-like, powder-like, granular, non-spherical particulate, crushed particulate, porous, continuous mass, fibrous, tubular, hollow fiber-like, etc., and may be any shape depending on the application of the molded product. Since the molded product is suitable for optical waveguides, it is preferably a sheet-like molded product (or plate-like molded product).

[0122] The method for obtaining a molded product from the composition is not particularly limited and includes methods such as forming a film on a substrate and then molding it by etching, injection molding, and casting polymerization. The method for obtaining a sheet-like molded product (or plate-like molded product) from the composition is not particularly limited and includes methods such as forming a film on a substrate.

[0123] In the casting polymerization method, for example, the composition is injected into a molding mold, degassing is performed as needed, and then the mixture is cured by heating in an oven, and the resulting molded product is removed. The removed molded product can also be further cured by irradiation with active energy rays.

[0124] When forming a cured film (sheet-like molded product) as a molded product on a substrate, the composition is applied to the substrate, and volatile components such as solvents are removed by heating and drying (pre-baking) and / or vacuum drying to form a coating film, and the cured film can be obtained by curing the coating film.

[0125] Examples of substrates include glass plates such as quartz glass, borosilicate glass, aluminasilate glass, soda-lime glass with a silica coating on the surface, and alkali-free glass; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon (silicon wafers); and substrates on which thin films of aluminum, silver, or silver / copper / palladium alloys are formed. Other cured films, resin films, transistors, circuits, etc., may be formed on these substrates.

[0126] Methods for coating the composition onto a substrate include spin coating, slit coating, slit and spin coating, and coating using an applicator.

[0127] When performing heat drying (pre-baking), the temperature is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When performing vacuum drying, it is preferable to do so under a pressure of 50 to 150 Pa and at a temperature in the range of 20 to 25°C.

[0128] The coating film can be cured, for example, by heating (post-bake). The heating temperature is preferably 60 to 250°C, more preferably 80 to 235°C. The heating time is preferably 1 minute to 72 hours, more preferably 10 minutes to 48 hours.

[0129] The thickness of the sheet-like molded product may be 50 μm or more, 100 μm or more, or 200 μm or more, and may be 5 mm or less, 3 mm or less, or 1 mm or less.

[0130] Since the cured product or molded product containing the same is formed from a composition, it can exhibit a high refractive index, and its refractive index can be controlled to a desired value by adjusting the composition of the composition, etc. The refractive index of the cured product or molded product containing the same at a wavelength of 550 nm may be 1.65 or higher, 1.68 or higher, 1.70 or higher, 1.72 or higher, 1.74 or higher, 1.76 or higher, or 1.78 or higher. The refractive index of the cured product or molded product containing the same at a wavelength of 550 nm may be, for example, 2.00 or lower, or 1.90 or lower.

[0131] The refractive index at 550 nm of a cured product or a molded product containing it can be measured, for example, by the following method. First, a coating film is formed on a substrate, and the coating film is cured to obtain a substrate with a cured film. Next, the transmission spectrum and reflection spectrum from 300 nm to 800 nm are measured on the substrate with the cured film 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). Then, the true reflection spectrum obtained by smoothing the transmission spectrum and reflection spectrum by subtracting the increase or decrease due to interference in the reflection spectrum is used to calculate the refractive index at 550 nm of the cured product or a molded product containing it from the value at 550 nm and the refractive index of the substrate, based on Fresnel's formula (e.g., Hecht Optics I, 5th edition, Maruzen Publishing, 2018, pp. 209-226). This allows the refractive index at 550 nm of the cured product or a molded product containing it to be determined.

[0132] The cured product or a molded product containing the same can be suitably used in optical waveguides (particularly as the core of an optical waveguide). [Examples]

[0133] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. In the following, unless otherwise specified, "parts" means "parts by mass".

[0134] [Synthesis Example 1] <Synthesis of compound (A-1)> Synthesis of compound (A-1a) [ka]

[0135] A four-necked flask equipped with a Liebig condenser and thermometer was placed under a nitrogen atmosphere. 30 parts of 1,6-naphthalenedithiol, 165 parts of acetone, 45 parts of pure water, and 139 parts of epichlorohydrin were added to the flask and stirred in an ice bath for 15 minutes. Subsequently, 15 parts of sodium hydroxide, 66 parts of acetone, and 203 parts of pure water were added to another flask and dissolved completely. These were then added dropwise to the four-necked flask over 1 hour. After the dropwise addition, the temperature was raised to 30°C and stirred at 30°C for 2 hours. The resulting mixture was purified to obtain 46 parts of the compound represented by formula (A-1a) (compound (A-1a)).

[0136] 1 1H-NMR analysis and LC-MS measurements were performed to confirm the formation of compound (A-1a). 1 ¹H-NMR (deuterated chloroform) δ: 8.37~8.39 (¹H), 7.85 (¹H), 7.39~7.70 (⁴H), 3.08~3.29 (⁵H), 2.94~2.98 (¹H), 2.57~2.81 (³H), 2.39~2.41 (¹H) LC-MS:[M+H] + =305.5

[0137] Synthesis of compound (A-1) [ka]

[0138] A four-necked flask equipped with a Liebig condenser and thermometer was placed under a nitrogen atmosphere. Three parts of compound (A-1a), 30 parts of methanol, 30 parts of toluene, 0.05 parts of acetic anhydride, and 3.8 parts of thiourea were added to the flask and stirred at room temperature for 24 hours. The resulting mixture was purified to obtain 2.5 parts of compound (compound (A-1)) represented by formula (A-1).

[0139] 1 1H-NMR analysis and LC-MS measurements were performed to confirm the formation of compound (A-1). 1 ¹H-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

[0140] [Examples 1-5 and Comparative Examples 1 and 2] <Preparation of Composition> The components shown in Table 1 were placed in a flask in the amounts (parts by mass) shown in Table 1. The flask was then fixed in a water bath maintained at 40°C, and the contents of the flask were stirred for 30 minutes to prepare the liquid compositions of Examples 1-5 and Comparative Example 1. Note that (B-3) becomes liquid when heated and remains liquid for a while even when left standing. Therefore, in Example 3, the composition was prepared by quickly adding (B-3), which had been heated to a liquid, to (A-1) while it was being stirred.

[0141] Furthermore, the components shown in Table 1 were placed in a flask in the amounts (unit: parts by mass) shown in Table 1, and 33 parts by mass of cyclopentanone were added. The flask was then fixed in a water bath maintained at 40°C, and the contents of the flask were stirred for 30 minutes to prepare the liquid composition of Comparative Example 2.

[0142] The compositions of Examples 1-5 and Comparative Examples 1 and 2 were visually observed for their appearance. The compositions of Examples 1-5 and Comparative Example 2 were colorless and transparent. On the other hand, the composition of Comparative Example 1 showed cloudiness and was undergoing hardening. Therefore, a sheet-like molded product was not prepared from the composition of Comparative Example 1.

[0143] The details of the abbreviations for the ingredients shown in Table 1 are as follows: (A) Component: Compound represented by formula (II) ·(A-1): Compound (A-1) (B) Component: Compound represented by formula (B) • (B-1): Tributylhexylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., liquid at 20°C) [ka] • (B-2): Tributyloctylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., solid at 20°C (melting point: 25°C)) [ka] • (B-3): Tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., solid at 20°C (melting point: 103°C)) [ka] • (B-4): Tetraoctylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., solid at 20°C (melting point: 42°C)) [ka] • (B-5): Trihexyltetradecylphosphonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd., liquid at 20°C) [ka] (b1) Component: Phosphonium salts other than component (B) • (b1-1): Tributylmethylphosphonium dimethyl phosphate (manufactured by Tokyo Chemical Industry Co., Ltd., liquid at 20°C) [ka] (b2) Components: Onium salts other than phosphonium salts • (b2-1): CXC-1821 (manufactured by KING INDUSTRIES INC., solid at 20°C) [ka]

[0144] <Evaluation Test> (1) Preparation of sheet-like molded products - 1 Sheet-like molded products were prepared using the compositions of Examples 1 to 5, which were colorless and transparent upon visual observation. First, each of the compositions of Examples 1 to 5 was dropped onto a release-treated glass plate. Next, the composition on the glass plate was sandwiched between other release-treated glass plates, and a sheet-like molded product was obtained by holding it at 90°C for 24 hours as a post-bake. One side of the glass plate was peeled off to obtain a glass plate on which the sheet-like molded products of Examples 1 to 5 were formed. The thickness of the sheet-like molded products of Examples 1 to 5 was measured using a stylus-type film thickness gauge (Bruker, "DekTak XT"), and the thickness was found to be 300 μm.

[0145] (2) Preparation of sheet-like molded products - 2 A sheet-like molded product was prepared using the composition of Comparative Example 2, which was colorless and transparent in visual observation. First, the composition of Comparative Example 2 was dropped between a glass plate and a 400 μm four-sided film applicator, and the composition was spread onto the glass plate with the four-sided film applicator. After heating at 80°C for 15 minutes as a pre-bake, the glass plate with the sheet-like molded product of Comparative Example 2 formed on it was obtained by holding it at 90°C for 24 hours. The thickness of the sheet-like molded product of Comparative Example 2 was measured using a stylus-type film thickness gauge (Bruker, "DekTak XT"), and the thickness was found to be 300 μm.

[0146] (3) Refractive index For the glass plates on which the sheet-like molded products prepared in (1) and (2) above were formed, the transmission and reflection spectra from 300 nm to 800 nm were measured using a visible-ultraviolet spectrophotometer ("V-650") with an integrating sphere unit ("ISV-922") ("V-650") manufactured by JASCO Corporation. The true reflection spectrum, obtained by smoothing the transmission and reflection spectra by subtracting the increase and decrease due to interference in the reflection spectrum, was used to calculate the refractive index of the sheet-like molded product at a wavelength of 550 nm based on the value at 550 nm and the refractive index of the alkali-free glass plate ("Eagle XG") manufactured by Corning, based on Fresnel's formula (Hect Optics I, 5th edition, Maruzen Publishing, 2018, pp. 209-226). The results are shown in Table 1.

[0147] (4) Resistance to yellowing The yellowing resistance of the sheet-like molded products of Examples 1-5 and Comparative Example 2 was evaluated. More specifically, the appearance of the sheet-like molded products was observed visually using glass plates on which the sheet-like molded products prepared in (1) and (2) above were formed, and the internal transmittance of the sheet-like molded products at a wavelength of 450 nm was measured. The results are shown in Table 1.

[0148] (5) Hayes Haze measurements were performed on the sheet-like molded articles of Examples 1-5 and Comparative Example 2. The haze in the visible light region (380 nm to 780 nm) of the obtained sheet-like molded articles (thickness 300 μm) was measured using a haze measuring device (Suga Test Instruments "HZ-2"). The standard light was D65 light. The results are shown in Table 1.

[0149] [Table 1]

[0150] As shown in Table 1, the compositions of Examples 1 to 5 exhibited a high refractive index in the cured product and were good in both appearance and internal transmittance. In addition, the cured products of the compositions of Examples 1 to 5 had a good haze of less than 2%, and no clouding was observed. In contrast, it was difficult to produce a sheet-like molded product from the composition of Comparative Example 1. Furthermore, although the refractive index of the composition of Comparative Example 2 was sufficiently high in the cured product, both the appearance and internal transmittance were insufficient. Moreover, the cured product of the composition of Comparative Example 2 had a haze of 3.0%, and clouding was also observed. From these results, it was confirmed that the compositions of the present invention can provide a cured product that exhibits a high refractive index and has excellent resistance to yellowing.

Claims

1. Compound (A) represented by formula (II), Compound (B) represented by formula (B), A composition containing the following: 【Chemistry 1】 [In formula (II), L １ｘ represents a single bond or a divalent group, and there are two L １ｘ They may be the same or different. A １ｘ represents an oxygen atom or a sulfur atom, and there are two A １ｘ They may be the same or different. However, if there are two A １ｘ At least one of them is a sulfur atom. mx represents either 0 or 1, and the two mx values ​​may be the same or different. nx represents an integer between 0 and 6. R １ｘ represents a monovalent substituent, R １ｘ If there are multiple R １ｘ They may be the same or different. R ２ｘ represents a hydrogen atom or a monovalent substituent, and the two Rs ２ｘ may be the same or different.] 【Chemistry 2】 [In formula (B), R ｂ１ , R ｂ２ , R ｂ３ , and R ｂ４ Each of these independently represents a monovalent hydrocarbon group which may have substituents. X － This represents a halide ion.

2. R ｂ１ , R ｂ２ , R ｂ３ , and R ｂ４ The composition according to claim 1, wherein the alkyl group has 1 to 16 carbon atoms, which may have substituents.

3. A composition according to claim 1 or 2, used in the manufacture of an optical waveguide.

4. A cured product of the composition according to claim 1 or 2.

5. A sheet-like molded article obtained by curing the composition according to claim 1 or 2.

6. An optical waveguide comprising the sheet-like molded product described in claim 5.

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