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

Abstract

The invention relates to a compound, 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 which can provide a cured product exhibiting a high refractive index and which has excellent alkali developability. The solution of the present invention is a composition containing a compound represented by formula (I), a compound having a group represented by formula (X), and a curing agent. In formula (I), L represents an optionally substituted branched alkylene group having 2-20 carbon atoms, and two L may be the same as or different from each other. A represents a hydrogen atom or a cation, and two A may be the same as or different from each other. And n represents an integer of 0-6. R represents a monovalent substituent, and when a plurality of R are present, the plurality of R may be the same as or different from each other. In formula (X), a ring Zx containing a sulfur atom as a constituent atom represents a 3-membered ring or a 4-membered ring. R2x represents a hydrogen atom or a monovalent substituent. And * represents a bonding position. # imgabs0 #

Description

Technical Field

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

[0002] In the field of optical devices, a high-refractive-index material is urgently desired. A lens can be obtained using a high-refractive-index material, and the optical path in an optical device can be controlled using the lens. In a solid-state imaging device, a lens is used for the purpose of improving the light condensing efficiency in each photoelectric conversion element, and in a display device, a lens is used for the purpose of improving the light extraction efficiency from pixels. Conventionally, various high-refractive-index materials have been developed (for example, Patent Document 1).

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: International Publication No. 2023 / 058449 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 that can provide a cured product exhibiting a high refractive index and has excellent alkali developability.

[0008] Means for Solving the Problems

[0009] The present invention provides the composition according to [1] to [5], the molded product according to [6], the cured product according to [7], the display device according to [8], the solid-state imaging device according to [9], and the compound according to

[10] .

[0010] [1] A composition comprising a compound represented by formula (I), a compound having a group represented by formula (X), and a curing agent.

[0011]

[0012] [In formula (I),

[0013] L represents a branched alkylene group having 2 to 20 carbon atoms which may have a substituent, and two Ls may be the same or different.

[0014] A represents a hydrogen atom or a cation, and two As may be the same or different.

[0015] n represents an arbitrary integer from 0 to 6.

[0016] R represents a monovalent substituent, and when there are a plurality of Rs, the plurality of Rs may be the same or different.]

[0017]

[0018] [In formula (X),

[0019] ring Z containing a sulfur atom as a constituent atom x represents a 3-membered ring or a 4-membered ring.

[0020] R 2x represents a hydrogen atom or a monovalent substituent.

[0021] * represents the bonding position.]

[0022] [2] The composition according to [1], wherein the compound represented by the aforementioned formula (I) is a compound represented by formula (I-1).

[0023]

[0024] [In formula (I-1),

[0025] A, n, and R represent the same meanings as described above.

[0026] m represents any integer from 1 to 6.

[0027] R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when there are a plurality of R 1 and R 2 when there are a plurality of them, a plurality of R 1 and R 2 may be the same or different.

[0028] Among them, when m is 1, at least one of R 1 and R 2 is an alkyl group having 1 to 6 carbon atoms, and when m is 2 or more, at least one of a plurality of R 1 and R 2 is an alkyl group having 1 to 6 carbon atoms.]

[0029] [3] The composition according to [1] or [2], wherein the aforementioned curing agent contains a photoacid generator.

[0030] [4] The composition according to any one of [1] to [3], wherein the compound having a group represented by formula (X) contains a compound represented by formula (II).

[0031]

[0032] [In formula (II),

[0033] L1x represents a single bond or a divalent group, and there are two Ls 1x which may be the same or different.

[0034] A 1x represents an oxygen atom or a sulfur atom, and there are two As 1x which may be the same or different. Among them, at least one of the two As 1x is a sulfur atom.

[0035] mx represents 0 or 1, and there are two mx which may be the same or different.

[0036] nx represents any integer from 0 to 6.

[0037] R 1x represents a monovalent substituent, R 1x in the case where there are multiple, there are multiple Rs 1x which may be the same or different.

[0038] R 2x represents a hydrogen atom or a monovalent substituent, and there are two Rs 2x which may be the same or different.]

[0039] [5] The composition according to any one of [1] to [4], which further contains an alicyclic epoxy compound.

[0040] [6] A molded article, which is formed by curing the composition according to any one of [1] to [5].

[0041] [7] A cured product of the composition according to any one of [1] to [5].

[0042] [8] A display device, which contains the cured product described in [7].

[0043] [9] A solid-state imaging device, which contains the cured product described in [7].

[0044]

[10] A compound represented by formula (I).

[0045]

[0046] [In formula (I),

[0047] L represents a branched alkylene group having 2 to 20 carbon atoms which may have substituents, and there are two Ls which may be the same or different.

[0048] A represents a hydrogen atom or a cation, and there are two As which may be the same or different.

[0049] n represents any integer from 0 to 6.

[0050] R represents a monovalent substituent, and when there are a plurality of Rs, the plurality of Rs may be the same or different.

[0051] Advantages of the Invention

[0052] According to the present invention, a composition capable of providing a cured product having a high refractive index and excellent alkali developability can be provided. The composition of the present invention tends to have excellent alkali developability even without pre-baking before development. The film-forming property and the like of the composition in some embodiments are also excellent. The solvent resistance (film thickness retention rate) and the like of the cured product of the composition in some embodiments are also excellent. In addition, according to the present invention, a molded article 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. Further, according to the present invention, a compound for such a composition can be provided. Detailed Embodiments

[0053] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0054] In this specification, a numerical range indicated by "~" represents a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in one numerical range can be replaced with the upper limit value or the lower limit value described in another stepwise described numerical range. In addition, in the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range can be replaced with the value shown in the examples.

[0055] In this specification, (meth)acrylate means acrylate or the corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl and (meth)acrylate.

[0056] In this specification, for the materials exemplified below, unless otherwise specified, one kind can be used alone within the range that meets the conditions, or two or more kinds can be used in combination. Regarding the content of each component, when there are a plurality of substances belonging to each component, unless otherwise specified, it means the total amount of the plurality of substances.

[0057] <Composition>

[0058] The composition of one embodiment contains a compound represented by formula (I) (hereinafter sometimes referred to as “component (A)”), a compound having a group represented by formula (X) (hereinafter sometimes referred to as “component (B)”), and a curing agent (hereinafter sometimes referred to as “component (C)”). The composition according to this embodiment can provide a cured product with a high refractive index and excellent alkali developability. The composition of this embodiment may further contain an alicyclic epoxy compound (hereinafter sometimes referred to as “component (D)”). The composition of this embodiment can be suitably used as, for example, a negative resist.

[0059] Component (A): The compound represented by formula (I)

[0060] The composition of this embodiment contains component (A). By including component (A) in the composition, the alkali developability of the resulting composition can be improved. In addition, component (A) has a tendency to have a high solubility in the solvent used in lithography (for example, propylene glycol monomethyl ether acetate (PGMEA)). Therefore, component (A) has a tendency not to precipitate easily in the solution and to be easily removed in the exposure and development process of the lithography method.

[0061]

[0062] In formula (I),

[0063] L represents a branched alkylene group having 2 to 20 carbon atoms which may have a substituent, and the two Ls may be the same or different.

[0064] A represents a hydrogen atom or a cation, and the two As may be the same or different.

[0065] n represents an arbitrary integer from 0 to 6.

[0066] R represents a monovalent substituent, and when there are a plurality of Rs, the plurality of Rs may be the same or different.

[0067] In the compound represented by formula (I), the two groups represented by formula (Z-1) may be bonded to any position of the 1st to 8th positions of the naphthalene ring. The group represented by formula (Z-1) on the naphthalene ring can be bonded to any two positions of the 1st to 4th positions (5th to 8th positions), or can be bonded to any one position of the 1st to 4th positions (5th to 8th positions) and any one position of the 5th to 8th positions (1st to 4th positions). The group represented by formula (Z-1) on the naphthalene ring is preferably bonded to any one position of the 1st to 4th positions (5th to 8th positions) and any one position of the 5th to 8th positions (1st to 4th positions).

[0068]

[0069] In formula (Z-1), L and A have the same meanings as described above. * represents the bonding position.

[0070] When the compound represented by formula (I) has one or more monovalent substituents represented by R, the monovalent substituent represented by R can be bonded to any position of the 1-8 positions of the naphthalene ring other than the bonding position of the group represented by formula (Z-1).

[0071] Examples of the branched alkylene group represented by L include methylmethylene, ethylmethylene, propylmethylene, butylmethylene, pentylmethylene, dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 2-methyltrimethylene, 2-methyltetramethylene, 2-methylpentamethylene, 3-methylhexamethylene, 4-methylheptamethylene, 4-methyloctamethylene, 5-methylnonamethylene, 5-methyldecamethylene, 6-methylundecamethylene, 7-methyldodecamethylene, 7-methyltridecamethylene, etc. The number of carbon atoms of the branched alkylene group including the carbon atoms of the substituent is 2-20, preferably 2-10, more preferably 2-7, and further preferably 2-5.

[0072] Examples of the substituents that the branched alkylene group may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; monovalent aromatic hydrocarbon groups such as phenyl group and naphthyl group, hydroxyl group; amino group; acetyl group; cyano group, etc.

[0073] Examples of the cation represented by A include monovalent cations, divalent cations, etc. Examples of the monovalent cation include alkali metal ions such as lithium ion, sodium ion, and potassium ion; ammonium ions such as tetrahydroammonium ion (NH4 + ), tetraalkylammonium ions, etc. Examples of the divalent cation include magnesium ion, calcium ion, etc. The divalent cation can form the bonds shown below within or between molecules, for example.

[0074]

[0075] A represents a divalent cation, L has the same meaning as described above. * represents the bonding position.

[0076] A is preferably a hydrogen atom or a monovalent cation, more preferably a hydrogen atom.

[0077] n is preferably any integer from 0 to 3, more preferably any integer from 0 to 2, further preferably 0 or 1, and particularly preferably 0.

[0078] R represents a monovalent substituent. When there are multiple Rs, the multiple Rs can be the same or different, and they can be the same. Examples of the monovalent substituent represented by R 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 thereof (e.g., aralkyl), etc.; a hydroxyl group; an amino group, a monomethylamino group, a monoethylamino group, a dimethylamino group, a diethylamino group, a methylethylamino group, etc., an amino group which may be substituted by one or two alkyl groups having 1 to 6 carbon atoms; 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 piperidyl group, a morpholinyl group, a piperazinyl group, an indolyl group, an isoindolyl group, a quinolinyl group, a thienyl group, a pyrrolyl group, a furyl group, etc.; a halogen atom; a nitro group; a cyano group; a carboxyl group; a sulfo group; a mercapto group; a formyl group; a -SF3 group; a -SF5 group. The methylene group (-CH2-) contained in the monovalent substituent may be replaced by -O-, -S-, -NR 1B -(R 1B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)., -CO-, or -SO2-. It should be noted that examples of the group obtained by replacing the methylene group (-CH2-) contained in the monovalent substituent with -O- include alkoxy groups having 1 to 12 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy; alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, methoxyethyl, etc.

[0079] Examples of the monovalent aliphatic chain hydrocarbon group include saturated or unsaturated aliphatic chain hydrocarbon groups. More specifically, examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl. The monovalent aliphatic chain hydrocarbon group may be linear or branched. The number of carbon atoms of the monovalent aliphatic chain hydrocarbon group is usually 1 to 20, preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 or 2.

[0080] Examples of the substituent that the monovalent aliphatic chain hydrocarbon group may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; a hydroxyl group; an amino group; an acetyl group; a cyano group, etc.

[0081] As a monovalent alicyclic hydrocarbon group, for example, a saturated or unsaturated alicyclic hydrocarbon group can be cited. More specifically, monocyclic alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, cyclodecyl, etc. can be cited; 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, tricyclo[5.3.1.1]dodecyl, etc. can be cited. The number of carbon atoms of the monovalent alicyclic hydrocarbon group is usually 3 to 20, preferably 3 to 10, more preferably 3 to 6, and further preferably 5 or 6.

[0082] As substituents that the monovalent alicyclic hydrocarbon group may have, for example, 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, decyl, etc. can be cited; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc.; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0083] The monovalent aromatic hydrocarbon group can be monocyclic or polycyclic. As the monovalent aromatic hydrocarbon group, for example, phenyl, naphthyl, anthryl, fluorenyl, etc. can be cited. The number of carbon atoms of the monovalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0084] As substituents that the monovalent aromatic hydrocarbon group may have, for example, 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, decyl, etc. can be cited; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc.; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0085] Component (A) is preferably a compound represented by formula (I-1).

[0086]

[0087] In formula (I-1),

[0088] A, n, and R represent the same meanings as described above.

[0089] m represents any integer from 1 to 6.

[0090] R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when there are multiple R 1 and R 2 When there are multiple, multiple R 1 and R 2 can be the same or different.

[0091] Among them, when m is 1, R1 and R 2 at least one of them is an alkyl group having 1 to 6 carbon atoms, and when m is 2 or more, there are a plurality of Rs 1 and R 2 at least one of them is an alkyl group having 1 to 6 carbon atoms.

[0092] In the compound represented by formula (I-1), two groups represented by formula (I-1-0) can be bonded to any position of the 1st to 8th positions of the naphthalene ring. The group represented by formula (I-1-0) on the naphthalene ring can be bonded to any two positions of the 1st to 4th positions (5th to 8th positions), or can be bonded to any one position of the 1st to 4th positions (5th to 8th positions) and any one position of the 5th to 8th positions (1st to 4th positions). The group represented by formula (I-1-0) on the naphthalene ring is preferably bonded to any one position of the 1st to 4th positions (5th to 8th positions) and any one position of the 5th to 8th positions (1st to 4th positions).

[0093]

[0094] In formula (I-1-0), A, m, R 1 , and R 2 have the same meanings as described above. * represents the bonding position.

[0095] When the compound represented by formula (I-1) has one or more monovalent substituents represented by R, the monovalent substituent represented by R can be bonded to any position of the 1st to 8th positions of the naphthalene ring other than the bonding position of the group represented by formula (I-1-0).

[0096] m is preferably any integer from 1 to 4, more preferably any integer from 1 to 3, and still more preferably 1 or 2.

[0097] As R 1 and R 2 The alkyl groups represented include, for example, methyl, ethyl, linear or branched propyl, linear or branched butyl, linear or branched pentyl, and linear or branched hexyl. The number of carbon atoms of the alkyl group is 1 to 6, preferably 1 to 4, and more preferably 1 to 2.

[0098] When m is 1, at least one of R 1 and R 2 is an alkyl group having 1 to 6 carbon atoms, and when m is 2 or more, there are a plurality of Rs 1 and R 2 at least one of them is an alkyl group having 1 to 6 carbon atoms. That is, the group represented by -[C(R 1 )(R 2 )]m- means a branched alkylene group. -[C(R 1 )(R2 ) The number of carbon atoms in the group represented by m-, including the carbon atoms of the substituent, is preferably 2 to 10, more preferably 2 to 7, and still more preferably 2 to 5. There are two -[C(R 1 )(R 2 )]m- groups may be the same or different.

[0099] Specific examples of the component (A) are shown below, but are not limited thereto.

[0100]

[0101]

[0102]

[0103] From the viewpoint of synthesis, the molecular weight of the component (A) is preferably 2000 or less, more preferably 1000 or less, and still more preferably 600 or less. From the viewpoint of volatility, the molecular weight of the component (A) is preferably 200 or more, more preferably 250 or more, and still more preferably 300 or more.

[0104] (A) component (compound represented by formula (I)) can be obtained, for example, by reacting a compound represented by formula (Ia) (e.g., naphthalene dithiol compound) with a compound represented by formula (Ib) (e.g., carboxylic acid compound having a haloalkyl group) in the presence of a base.

[0105]

[0106] n and R represent the same meanings as described above.

[0107]

[0108] L and A represent the same meanings as described above, and X represents a halogen atom. Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.

[0109] 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 (1,8-diazabicyclo[5.4.0]undec-7-ene), DABCO (1,4-diazabicyclo[2.2.2]octane), pyridine, 2,6-dimethylpyridine, 2,6-di-tert-butylpyridine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, and tetramethylammonium chloride. The amount of the base used is, for example, 0.0001 to 10 moles, preferably 0.001 to 5 moles, more preferably 0.01 to 4 moles, and still more preferably 0.1 to 3 moles, relative to 1 mole of the compound represented by formula (Ia).

[0110] The amount of the compound represented by formula (Ib) used is, for example, 0.01 to 20 moles, preferably 0.5 to 15 moles, relative to 1 mole of the compound represented by formula (Ia). In this step, the reaction may also be carried out using two or more compounds represented by formula (Ib).

[0111] The reaction between the compound represented by formula (Ia) and the compound represented by formula (Ib) is preferably carried out in a solvent. Examples of the solvent include organic solvents such as ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, alcohols, glycol dimethyl ethers, esters, aliphatic nitriles, sulfoxides, and amides, in addition to water. Examples of the organic solvent are shown below.

[0112] 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.

[0113] Aromatic hydrocarbons: benzene, toluene, xylene, mesitylene, naphthalene, anisole, nitrobenzene, aniline, tetralin, durene, etc.

[0114] Halogenated aromatic hydrocarbons: chlorobenzene, dichlorobenzene, chloronaphthalene, etc.

[0115] Aliphatic hydrocarbons: pentane, hexane, heptane, etc.

[0116] Halogenated aliphatic hydrocarbons: dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, tetrachloroethylene, etc.

[0117] Ethers: diethyl ether, diisopropyl ether, methyl tert-butyl ether, cyclopentyl methyl ether, diphenyl ether, dimethoxyethane, dioxane, etc.

[0118] Alcohols: methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, hexafluoroisopropanol, etc.

[0119] Glycol dimethyl ethers: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, etc.

[0120] Esters: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc.

[0121] Aliphatic nitriles: acetonitrile, etc.

[0122] Sulfoxides: dimethyl sulfoxide, sulfolane, etc.

[0123] Amides: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0124] The temperature of the reaction between the compound represented by formula (Ia) and the compound represented by formula (Ib) can 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.

[0125] By operating as described above, the component (A) (the compound represented by formula (I)) can be obtained. When using the component (A), the component (A) can be used after separation or directly without separation.

[0126] From the aspect of easily obtaining the effects of the present invention sufficiently, based on the total amount of the solid components of the composition, the content of the component (A) can be, for example, 10 to 70% by mass. Based on the total amount of the composition, the content of the component (A) is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, preferably 65% by mass or less, more preferably 55% by mass or less, and further preferably 45% by mass or less.

[0127] The total amount of the solid components of the composition refers to the total of the components contained in the composition excluding the solvent. The content of each component in the solid components of the composition can be measured by known analytical means such as liquid chromatography and gas chromatography. The content of each component in the solid components of the composition can also be calculated based on the formulation during the preparation of the composition.

[0128] (B) component: a compound having a group represented by formula (X)

[0129] The composition of the present embodiment contains the component (B). By making the composition contain the component (B), a cured product having a high refractive index can be provided.

[0130] Lithography is a method in which a composition is coated on a substrate, dried as needed to form a coating film (coating layer), the coating film is exposed through a photomask, whereby the exposed portion is cured, and the exposed coating film is developed (the unexposed portion is removed). However, after pattern exposure, sometimes a heat treatment is performed on the exposed coating film before development (referred to as pre-development baking, post-exposure baking, post-exposure bake (PEB), etc.). For a composition containing a compound having an epoxy group or an oxetanyl group, if pre-development baking is not performed, there is a tendency that it is difficult to obtain a patterned cured film (cured layer) by development. On the other hand, according to the research of the inventors of the present application, it has been found that in the composition of the present embodiment containing the component (B), there is a tendency that a patterned cured film can be easily obtained by development even without pre-development baking. Therefore, by making the composition contain the component (B), the step of pre-development baking can be omitted in the steps of exposure and development, and the productivity of the molded article can be improved.

[0131]

[0132] In formula (X),

[0133] Ring Z containing a sulfur atom as a constituent atom x represents a 3-membered ring or a 4-membered ring.

[0134] R 2x represents a hydrogen atom or a monovalent substituent.

[0135] * represents the bonding position.

[0136] Ring Z containing a sulfur atom as a constituent atom x is a 3-membered ring or a 4-membered ring. That is, ring Z x is a 3-membered ring containing a sulfur atom as a constituent atom (thiirane ring) or a 4-membered ring containing a sulfur atom as a constituent atom (tetrahydrothiophene ring). The group represented by formula (X) can be, for example, one group selected from the group consisting of the group represented by formula (Xa), the group represented by formula (Xb-1), and the group represented by formula (Xb-2). That is, the compound having the group represented by formula (X) can be a compound having at least one thiiranyl group or tetrahydrothiophenyl group.

[0137]

[0138] In formula (Xa), formula (Xb-1), and formula (Xb-2), R 2x represents the same meaning as described above.

[0139] As the monovalent substituent represented by R 2x substituents similar to the monovalent substituent represented by R can be exemplified.

[0140] The group represented by formula (X) is preferably a group represented by formula (X1).

[0141]

[0142] In formula (X1),

[0143] ring Z x and R 2x have the same meanings as described above.

[0144] L 1x represents a single bond or a divalent group.

[0145] * represents the bonding position.

[0146] The group represented by formula (X1) can be, for example, one group selected from the group consisting of a group represented by formula (X1a), a group represented by formula (X1b-1), and a group represented by formula (X1b-2).

[0147]

[0148] In formula (X1a), formula (X1b-1), and formula (X1b-2), L 1x and R 2x have the same meanings as described above.

[0149] As the divalent group represented by L 1x , for example, 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 hydrocarbon group formed by a combination thereof (for example, an arylalkylene group), etc. The methylene group (-CH2-) contained in the divalent group may be substituted by -O-, -S-, -NR A -(R A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.), -CO-, or -SO2-.

[0150] As the divalent aliphatic chain hydrocarbon group, for example, a saturated or unsaturated aliphatic chain hydrocarbon group can be mentioned. More specifically, methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl, undecanediyl, dodecanediyl, tridecanediyl, tetradecanediyl, pentadecanediyl, hexadecanediyl, heptadecanediyl, octadecanediyl, nonadecanediyl, icosanediyl, etc. alkane diyls can be mentioned. The divalent aliphatic chain hydrocarbon group can be linear or branched. The number of carbon atoms of 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.

[0151] Examples of the substituents that the divalent aliphatic chain hydrocarbon group may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0152] 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, cyclodecanediyl; 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, tricyclo[5.3.1.1]dodecanediyl, etc. The number of carbon atoms of the divalent alicyclic hydrocarbon group is usually 3 to 20, preferably 3 to 10, more preferably 3 to 6, and further preferably 5 or 6.

[0153] Examples of the 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 group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0154] The divalent aromatic hydrocarbon group may be monocyclic or polycyclic. Examples of the divalent aromatic hydrocarbon group include phenylene group, naphthylene group, anthracenediyl group, fluorenediyl group, etc. The number of carbon atoms of the divalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0155] Examples of the 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 group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0156] From the viewpoint of the high refractive index of the cured product, the component (B) is preferably a compound containing an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring; aromatic heterocycles such as furan ring, pyrrole ring, benzofuran ring, thiophene ring, benzothiophene ring, indole ring, pyridine ring, quinoline ring, isoquinoline ring, pyridazine ring, pyrimidine ring, and triazine ring. The aromatic ring is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring.

[0157] From the viewpoint of the high refractive index of the cured product, the component (B) is preferably a compound represented by the formula (II).

[0158]

[0159] In formula (II),

[0160] L 1x represents a single bond or a divalent group, and there are two Ls 1x which may be the same or different.

[0161] A 1x represents an oxygen atom or a sulfur atom, and there are two As 1x which may be the same or different. Among them, at least one of the two As 1x is a sulfur atom.

[0162] mx represents 0 or 1, and there are two mx which may be the same or different.

[0163] nx represents any integer from 0 to 6.

[0164] R 1x represents a monovalent substituent, and R 1x when there are multiple ones, the multiple Rs 1x may be the same or different.

[0165] R 2x represents a hydrogen atom or a monovalent substituent, and there are two Rs 2x which may be the same or different.

[0166] In the compound represented by formula (II), the two groups represented by formula (II-c) may be bonded to any position of the 1-8 positions of the naphthalene ring. For example, the groups represented by formula (II-c) on the naphthalene ring may be bonded to any two positions of the 1-4 positions (5-8 positions), or may be bonded to any one position of the 1-4 positions (5-8 positions) and any one position of the 5-8 positions (1-4 positions). The groups represented by formula (II-c) on the naphthalene ring are preferably bonded to any one position of the 1-4 positions (5-8 positions) and any one position of the 5-8 positions (1-4 positions).

[0167]

[0168] In formula (II-c), L 1x , A 1x , mx, and R 2x represent the same meanings as described above, and * represents the bonding position.

[0169] When the compound represented by formula (II) has one or more R 1x representing monovalent substituents, the monovalent substituents represented by R 1x may be bonded to any position of the 1-8 positions of the naphthalene ring other than the bonding positions of the groups represented by formula (II-c).

[0170] L 1x represents a single bond or a divalent group, and there are two Ls 1x which may be the same or different. In the compound represented by formula (II), there are two Ls 1x In this regard, at least one of them is preferably an alkylene group, and more preferably both are alkylene groups. In this case, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 or 2.

[0171] A 1x represents an oxygen atom or a sulfur atom, and there are two As 1x which may be the same or different. Among them, at least one of the two As 1x is a sulfur atom. In the compound represented by formula (II), there are two As 1x In this regard, both are preferably sulfur atoms. As the number of sulfur atoms as A 1x increases, there is a tendency to provide a cured product that exhibits a higher refractive index and has more excellent solvent resistance.

[0172] mx represents 0 or 1, and the two mx may be the same or different. In the compound represented by formula (II), it is preferred that both of the two mx are 0.

[0173] nx represents any integer from 0 to 6. nx is preferably any integer from 0 to 3, more preferably any integer from 0 to 2, still more preferably 0 or 1, and particularly preferably 0.

[0174] R 1x represents a monovalent substituent. When there are multiple Rs 1x the multiple Rs 1x may be the same or different. The monovalent substituent represented by R 1x may exemplify the same substituents as those represented by R.

[0175] R 2x represents a hydrogen atom or a monovalent substituent, and the two Rs 2x may be the same or different. The monovalent substituent represented by R 2x may exemplify the same substituents as those represented by R. In the compound represented by formula (II), the two Rs 2x are 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, still 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.

[0176] As the component (B) (the compound represented by the formula (II)), for example, compounds represented by the formula (II-A), the formula (II-B), the formula (II-C), the formula (II-D), the formula (II-E), and the formula (II-F) can be mentioned. L in the formula (II-A), the formula (II-B), the formula (II-C), the formula (II-D), the formula (II-E), and the formula (II-F) 1x , A 1x , mx, nx, R 1x , and R 2x represent the same meanings as described above.

[0177]

[0178] In the formula (II-A), the formula (II-B), the formula (II-C), the formula (II-D), the formula (II-E), and the formula (II-F), for the two L 1x , at least one is preferably an alkylene group, and more preferably both are alkylene groups. In this case, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 or 2.

[0179] In the formula (II-A), the formula (II-B), the formula (II-C), the formula (II-D), the formula (II-E), and the formula (II-F), the two mx are each independently 0 or 1, and preferably 0. In the formula (II-A), the formula (II-B), the formula (II-C), the formula (II-D), the formula (II-E), and the formula (II-F), it is preferred that both of the two mx are 0.

[0180] In the formula (II-A), the formula (II-B), the formula (II-C), the formula (II-D), the formula (II-E), and the formula (II-F), nx is each independently any integer from 0 to 6, preferably any integer from 0 to 3, more preferably any integer from 0 to 2, still more preferably 0 or 1, and particularly preferably 0.

[0181] In the formula (II-A), the formula (II-B), the formula (II-C), the formula (II-D), the formula (II-E), and the formula (II-F), the two A 1x are each independently an oxygen atom or a sulfur atom. Among them, at least one of the two A 1x is a sulfur atom. A 1x is preferably both sulfur atoms.

[0182] In the formula (II-A), the formula (II-B), the formula (II-C), the formula (II-D), the formula (II-E), and the formula (II-F), the two R 2xEach 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, still 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. There are two Rs 2x are preferably the same.

[0183] Specific examples of the component (B) (the compound represented by the formula (II)) are shown below, but are not limited thereto.

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191] From the viewpoint of synthesis, the molecular weight of the component (B) is preferably 2000 or less, more preferably 1000 or less, and still more preferably 750 or less. From the viewpoint of volatility, the molecular weight of the component (B) is preferably 50 or more, more preferably 100 or more, and still more preferably 150 or more.

[0192] The compound represented by the formula (II) as the component (B) can be obtained by synthesizing the compound represented by the formula (II-1) and reacting the compound represented by the formula (II-1) with a sulfurizing agent.

[0193]

[0194] In the formula (II-1), L 1x , mx, nx, R 1x , and R 2x have the same meanings as described above (for the formula (I)).

[0195] The compound represented by the formula (II-1) can be obtained, for example, by a method including a step of reacting the compound represented by the formula (II-1a) with the compound represented by the formula (II-1b).

[0196]

[0197] In the formula (II-1a), nx and R 1x have the same meanings as described above.

[0198]

[0199] In formula (II-1b), L 1x , mx, and R 2x have the same meanings as described above, and X 1X represents a leaving group.

[0200] 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. As the base, the same bases as those used in the reaction between the compound represented by formula (Ia) and the compound represented by formula (Ib) can be exemplified. With respect to 1 mole of the compound represented by formula (II-1a), the amount of the base used can be, for example, 0.0001 to 10 moles, preferably 0.001 to 5 moles, more preferably 0.01 to 4 moles, and further preferably 0.1 to 3 moles.

[0201] With respect to 1 mole of the compound represented by formula (Ia), the amount of the compound represented by formula (Ib) used can be, for example, 0.01 to 20 moles, preferably 0.5 to 15 moles. In this step, the reaction can also be carried out using two or more compounds represented by formula (Ib).

[0202] In addition, two or more bases can also be used in combination. In the case of using in combination, a combination of 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 metal alkoxides such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium tert-butoxide, potassium tert-butoxide is preferred, and a combination of a bicarbonate and a metal hydroxide is more preferred. In the case of using in combination, the two can be added simultaneously or added stepwise.

[0203] In the compound represented by formula (II-1b), as the leaving group represented by X 1X , halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom can be mentioned; alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, trifluoromethylsulfonyl group, perfluoroethylsulfonyl group, perfluoropropylsulfonyl group, perfluorobutylsulfonyl group; arylsulfonyl groups such as phenylsulfonyl group, p-toluenesulfonyl group, p-fluorophenylsulfonyl group, pentafluorophenylsulfonyl group, etc. As a specific example of the compound represented by formula (II-1b), epihalohydrin compounds (L 1x is methylene, mx is 0, R 2xa compound in which Y is a hydrogen atom and X is a halogen atom). The amount of the compound represented by the formula (II-1b) used is, for example, 0.01 to 20 moles, preferably 0.5 to 15 moles, relative to 1 mole of the compound represented by the formula (II-1a). In this step, the reaction can also be carried out using two or more compounds represented by the formula (II-1b).

[0204] The reaction between the compound represented by the formula (II-1a) and the compound represented by the formula (II-1b) is preferably carried out in a solvent. Examples of the solvent include the same solvents as those used in the reaction between the compound represented by the formula (Ia) and the compound represented by the formula (Ib).

[0205] The reaction temperature between the compound represented by the formula (II-1a) and the compound represented by the formula (II-1b) can 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.

[0206] By operating as described above, the compound represented by the formula (II-1) can be obtained. When the compound represented by the formula (II-1) obtained is used in the synthesis of the compound represented by the formula (II), the compound represented by the formula (II-1) can be used after separation or directly without separation.

[0207] The compound represented by the formula (II) can be obtained, for example, by a method including a step of reacting the compound represented by the formula (II-1) with a sulfurizing agent.

[0208] The reaction between the compound represented by the formula (II-1) and the sulfurizing agent is a reaction in which the sulfurizing agent replaces the oxygen atom of the epoxy ring or oxetanyl ring in the compound represented by the formula (II-1) with a sulfur atom to form a thiirane ring (episulfide ring) or a thietane ring. Examples of the sulfurizing agent include thiourea, methylthiourea, dimethylthiourea, trimethylthiourea, tetramethylthiourea, tetraethylthiourea, ethylenethiourea, phenylthiourea, diphenylthiourea, tolylthiourea, xylylthiourea, sodium thiocyanate, potassium thiocyanate, etc. The amount of the sulfurizing agent used can be arbitrarily adjusted according to the oxygen atom to be replaced. The amount of the sulfurizing agent used is, for example, 0.01 to 20 moles, preferably 0.5 to 10 moles, relative to 1 mole of the compound represented by the formula (II-1). In addition, by adjusting the amount of the sulfurizing agent used, the reaction temperature, the reaction time, etc., two oxygen atoms in the compound represented by the formula (II-1) can be replaced with sulfur atoms, or one oxygen atom in the compound represented by the formula (II-1) can be replaced with a sulfur atom.

[0209] The reaction of the compound represented by formula (II-1) with a sulfurizing agent is preferably carried out in a solvent. As the solvent, the same solvents as those exemplified in the reaction of the compound represented by formula (II-1a) with the compound represented by formula (II-1b) can be exemplified. For the reaction of the compound represented by formula (II-1) with a sulfurizing agent, for example, it can be -80 to 200 °C, preferably -40 to 100 °C, more preferably -20 to 80 °C, and further preferably -5 to 60 °C.

[0210] In order to inhibit the polymerization of the resulting compound represented by formula (II), a polymerization inhibitor can be added to the reaction system. As the polymerization inhibitor, for example, acids, acid anhydrides, etc. can be cited. More specifically, examples include:

[0211] Inorganic acidic compounds such as nitric acid, hydrogen chloride (hydrochloric acid), perchloric acid, hypochlorous acid, chlorine dioxide, hydrofluoric acid, sulfuric acid, fuming sulfuric acid, sulfonyl chloride, boric acid, arsenic acid, arsenous acid, pyroarsenic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphoryl chloride, phosphoryl bromide, phosphorus sulfide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, hydrocyanic acid, chromic acid, nitric anhydride, sulfuric anhydride, boron oxide, arsenic acid pentoxide, diphosphorus 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, cesium dihydrogen phosphate;

[0212] 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, di(thiodipropionic acid) acetic acid, maleic acid, benzoic acid, phenylacetic acid, o-toluic acid, m-toluic acid, p-toluic acid, salicylic acid, 2-methoxybenzoic acid, 3-methoxybenzoic acid, benzoylbenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, benzilic acid, α-naphthoic acid, β-naphthoic acid, acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, trifluoroacetic anhydride;

[0213] Phosphoric acids such as mono-, di- and tri-methyl phosphates, mono-, di- and tri-ethyl phosphates, mono-, di- and tri-isobutyl phosphates, mono-, di- and tri-butyl phosphates, mono-, di- and tri-lauryl phosphates and phosphorous acids obtained by converting the phosphate moiety thereof into a phosphite moiety;

[0214] Organophosphorus compounds such as dialkyldithiophosphoric acids represented by dimethyldithiophosphoric acid;

[0215] Phenols such as phenol, catechol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 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, etc.;

[0216] 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, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 4B acid, diamino stilbene sulfonic acid, biphenyl sulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, peri acid, Laurent acid, phenyl J acid, etc.

[0217] Relative to 1 mole of the compound represented by formula (II), the amount of the polymerization inhibitor used can be, for example, 0.0001 to 1.0 mole, preferably 0.001 to 0.5 mole, more preferably 0.01 to 0.25 mole, and further preferably 0.05 to 0.15 mole. Among them, the polymerization inhibitor is preferably acetic acid, acetic anhydride, maleic acid, maleic anhydride, phosphoric acid, alkali metal hydrogen phosphate, or alkali metal dihydrogen phosphate.

[0218] For the product solution after the reaction, by washing with an acidic aqueous solution, the stability over time of the compound represented by formula (II) obtained can be improved. Specific examples of the acid used in the acidic aqueous solution include the acids exemplified above as polymerization inhibitors. This acid can be used alone or in combination of two or more. There is a tendency for this acidic aqueous solution to generally exhibit an effect at pH 6 or lower, but a more effective range is pH 3 or lower. 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.

[0219] In addition, in order to improve the stability of the compound represented by formula (II), a hydrogen sulfide adsorbent can also be used. As the hydrogen sulfide adsorbent, for example, iron(III) hydroxide, zinc oxide, KNK-301 (a zinc oxide-based adsorbent, manufactured by Kureha Corporation), NIONON 202A (an iron oxide-based adsorbent, manufactured by Ichii Seisakusho Co., Ltd.), LIMONI C (an iron hydroxide-based, manufactured by Japan Limonite Co., Ltd.), etc. can be cited. The hydrogen sulfide adsorbent can be added during the reaction or added and used during the purification after the reaction.

[0220] From the aspect of easily and sufficiently obtaining the effects of the present invention, based on the total amount of the solid components of the composition, the content of component (B) can be, for example, 10 to 90% by mass. Based on the total amount of the composition, the content of component (B) is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 45% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 65% by mass or less.

[0221] (C) Component: Curing agent

[0222] The composition of the present embodiment contains component (C). Component (C) is not particularly limited as long as it can initiate the polymerization of component (B), but preferably contains a compound that generates an acid or a base by irradiation with active energy rays to enable cationic polymerization or anionic polymerization of component (B). That is, component (C) preferably contains a photoacid generator or a photobase generator, and more preferably contains a photoacid generator. A photoacid generator is also called a photo cationic polymerization initiator. A photobase generator is also called a photoanionic polymerization initiator.

[0223] A photoacid generator is a compound that can release a substance that initiates cationic polymerization by irradiation with active energy rays. Examples of the photoacid generator include aromatic diazonium salts, aromatic sulfonium salts, aliphatic sulfonium salts, aromatic iodonium salts, pyridinium salts, cyclopentadienyliron(II) complexes, etc. When the photoacid generator is an onium salt, examples of the counter anion include hexafluoroantimonate, hexafluorophosphate, P(F) x (Rf) 6-x - (Rf represents a perfluoroalkyl group. x represents an integer from 1 to 5.), tetrafluoroborate, tetrakis(pentafluorophenyl)borate, etc.

[0224] A photobase generator is a compound that can release a substance that initiates anionic polymerization by irradiation with active energy rays. Examples of the photobase generator include ammonium salts, DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) salts, DBN (1,5-diazabicyclo[4.3.0]non-5-ene) salts, biguanide salts, aromatic dimethylureas, aliphatic dimethylureas, guadinine salts, phosphazene salts, imidazole salts, etc.

[0225] Regarding the content of component (C), based on 100 parts by mass of the total amount of component (B) and component (D) described later, from the viewpoints of improving solvent resistance, alkali developability, and / or heat resistance, it is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and further preferably 1.0 part by mass or more. From the viewpoints of making the alkali developability and / or heat resistance of the composition good, it is preferably 10 parts by mass or less, more preferably 9 parts by mass or less, and further preferably 8 parts by mass or less.

[0226] (D) Component: Alicyclic Epoxide

[0227] The composition of this embodiment may further contain component (D). Component (D) may be a curable compound. By making the composition further contain component (D), there is a tendency for the solvent resistance of the cured product to be more excellent.

[0228] (D) Component can be used without particular limitation as long as it is a compound having an alicyclic ring and an epoxy group in the molecule. Component (D) is preferably a compound having a structure in which at least one alicyclic unsaturated hydrocarbon is epoxidized. As the alicyclic unsaturated hydrocarbon, for example, hydrocarbons having a cyclopentene skeleton, hydrocarbons having a cyclohexene skeleton, etc. can be cited. The alicyclic unsaturated hydrocarbon can be a monocyclic compound or a fused polycyclic compound. Component (D) is preferably a compound having at least two (more than 2) structures in which alicyclic unsaturated hydrocarbons are epoxidized in one molecule. The number of structures in which alicyclic unsaturated hydrocarbons are epoxidized is preferably eight or less (8 or less), more preferably six or less (6 or less), and further preferably four or less (4 or less) in one molecule.

[0229] As specific examples of component (D), for example, Celloxide 2021P, Celloxide 8010, Celloxide 2081, Celloxide 2000, EHPE3150, Epolead GT401, Cyclomer M100 (all manufactured by Daicel Corporation), EPOCHALIC (Japanese for "エポカリック") THI-DE, EPOCHALIC DE-102, EPOCHALIC DE-103 (all manufactured by ENEOS Corporation) can be cited. Among them, component (D) is preferably Celloxide 2021P, Celloxide 8010, Celloxide 2081, Epolead GT401, EPOCHALIC THI-DE, EPOCHALIC DE-102, or EPOCHALIC DE-103 as a compound having at least two structures in which alicyclic unsaturated hydrocarbons are epoxidized in one molecule, and more preferably Celloxide 2021P, Celloxide 8010, Celloxide 2081, or EPOCHALIC THI-DE.

[0230] The molecular weight of component (D) is preferably 3000 or less, more preferably 2000 or less, further preferably 1000 or less, and particularly preferably 500 or less. The molecular weight of component (D) is preferably 50 or more, more preferably 100 or more, and further preferably 150 or more.

[0231] From the aspect of easily and sufficiently obtaining the effects of the present invention, based on the total amount of the solid components of the composition, the content of component (D) can be, for example, 1 to 30% by mass. Based on the total amount of the composition, the content of component (D) is preferably 3% by mass or more, more preferably 5% by mass or more, preferably 20% by mass or less, and more preferably 15% by mass or less.

[0232] As other components contained in the composition, for example, resins, curable compounds other than component (B) and component (D), solvents, additives, etc. can be mentioned. As additives, for example, polymerization inhibitors, inorganic particles, fillers, polymerization initiator aids, sensitizers, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, ultraviolet absorbers, antioxidants, dispersants, etc. can be mentioned.

[0233] (Resin)

[0234] The composition may contain one or more resins. By making the composition contain a resin, developability can be imparted to the cured product of the composition, or the mechanical properties and / or optical properties of the cured product and the molded article containing the same can be adjusted. As the resin, for example, thermoplastic resins and curable resins can be mentioned. The curable resin can be a photocurable resin that is cured by irradiation with active energy rays or a thermosetting resin that is cured by heat.

[0235] 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 can also be used as polymer blends or polymer alloys.

[0236] As curable resins, resins having a photopolymerizable group or a thermopolymerizable group can be mentioned. More specifically, for example, (meth)acrylic resins, epoxy resins, melamine resins, unsaturated polyester resins, phenolic resins, urea resins, alkyd resins, polyimide resins, etc. can be mentioned.

[0237] As other examples of the resin, an alkali-soluble resin can be cited. By including an alkali-soluble resin in the composition, developability can be further imparted 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, resins having a carboxyl group and / or a phenolic hydroxyl group can be cited.

[0238] 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 still more preferably 30 to 140 mgKOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the alkali-soluble resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

[0239] In addition, as other examples of the resin, a high refractive index resin can be cited. The so-called high refractive index resin refers to a resin having a refractive index of 1.60 or more at a wavelength of 550 nm.

[0240] The weight average molecular weight (Mw) of the resin measured by gel permeation chromatography (GPC) in terms of standard polystyrene can be, for example, 500 to 2,000,000, 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 raw materials used, the charging method, the reaction temperature, and the time.

[0241] When the composition contains a resin, based on the total amount of the solid components of the composition, the content of the resin 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.

[0242] (Curing compound other than component (B) and component (D))

[0243] The composition may contain one or more curing compounds other than component (B) and component (D). By including a curing compound other than component (B) and component (D) in the composition, the viscosity or solvent resistance of the composition can be adjusted, and the mechanical properties and / or optical properties of the obtained cured product and the molded article containing the same can be adjusted.

[0244] Examples of the curing compound other than component (B) and component (D) include, for example, an epoxy compound other than component (B) and component (D), an oxetane compound other than component (B), a hydroxyl compound, a vinyl ether compound, an allyl compound, a thiol compound, a polyphenol compound, an isothiocyanate compound, an acid anhydride, and the like.

[0245] When the composition contains a curable compound other than the component (B) and the component (D), based on the total amount of the solid components of the composition, the content of the curable compound other than the component (B) and the component (D) 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.

[0246] (Solvent)

[0247] The composition may contain one or two or more solvents. The solvent is preferably a solvent capable of dissolving or dispersing the component (B), and more preferably a solvent capable of further dissolving or dispersing other components other than the component (B). Examples of the solvent include the solvents (organic solvents) exemplified in the reaction of the compound represented by the formula (Ia) and the compound represented by the formula (Ib), ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0248] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexyl acetate, γ-butyrolactone, and the like.

[0249] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methylanisole, and the like.

[0250] Examples of the 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, ethyl 2-ethoxy-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, diethylene glycol monobutyl ether acetate, etc.

[0251] Examples of the ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, etc.

[0252] Examples of the alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol, etc.

[0253] Examples of the aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, etc.

[0254] Examples of the amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0255] When the composition contains a solvent, based on 100 parts by mass of the total amount of the solid components of the composition, 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, and more preferably 500 parts by mass or less. When the composition contains a solvent, the solid component concentration of the composition is preferably 5 to 60% by mass, and more preferably 10 to 50% by mass.

[0256] <Cured product and molded product>

[0257] The cured product of one embodiment is the cured product of the composition. The molded product of one embodiment is formed by curing the composition and contains the cured product of the composition. Since the composition has excellent film-forming properties and the like, it can be suitably used as a curable material for producing a cured product or a molded product containing the same. The cured product can be obtained by curing the component (B), the component (D), etc. in the composition by using at least one of irradiation with active energy rays and heat (preferably irradiation with active energy rays). The shape of the molded product containing the cured product is not particularly limited and may include a film shape, a plate shape, a lens shape, a powder shape, a granular shape, a non-spherical particle shape, a crushed particle shape, a porous shape, a massive continuum, a fibrous shape, a tubular shape, a hollow filament shape, etc., and can be any shape corresponding to the use of the molded product, etc.

[0258] As a method for obtaining a molded product from the composition, there is no particular limitation, and examples thereof include a method of forming a film on a substrate and then performing molding by etching or the like, an injection molding method, a casting polymerization molding method, etc.

[0259] In the casting polymerization molding method, for example, the composition is poured into a molding die, degassed as needed, and then cured by heating in an oven, and the obtained molded product is taken out. It is also possible to further irradiate the taken-out molded product with active energy rays to additionally perform curing.

[0260] In the case of forming a film as a molded product on a substrate, the composition can be coated on the substrate, dried as needed to form a coating film (coating layer), and the coating film is cured to obtain a molded product as a cured film (cured layer). The molded product can also be a patterned cured film. The patterned cured film can be obtained by patterning using a method such as photolithography, inkjet method, printing method, etc. The patterning method can be, for example, photolithography. Photolithography is the following method: the composition is coated on a substrate, dried as needed to form a coating film, and the coating film is exposed through a photomask, whereby the exposed portion is cured, and the exposed coating film is developed.

[0261] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass obtained by coating the surface with silica, and non-alkali glass; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; substrates obtained by forming an aluminum, silver, silver / copper / palladium alloy thin film, etc. on these substrates. Examples of the coating method of the composition on the substrate include a spin coating method, a slit coating method, a slit and spin coating method, etc.

[0262] The light source used during exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, a band-pass filter can be used to selectively extract light near 436 nm, near 408 nm, or near 365 nm from the light with wavelengths in these ranges according to the absorption wavelength of the photoinitiator. Specific examples of the light source include mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc.

[0263] After pattern exposure, it is also possible to perform a heating (pre-baking before development) treatment on the coated film after exposure before development. For a composition containing a compound having an epoxy group or an oxetanyl group, if pre-baking before development is not performed, there is a tendency that it is difficult to obtain a patterned cured film by development. On the other hand, according to the research of the inventors of the present application, it has been found that in the composition of the present embodiment containing the component (B) (a compound having a group represented by the formula (X)), there is a tendency that a patterned cured film can be easily obtained by development even without pre-baking before development. Therefore, by using the composition of the present embodiment, the pre-baking before development process can be omitted in the exposure and development processes, and the productivity of the molded article can be improved.

[0264] As the developer used during development, for example, an aqueous solution containing an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, etc., a solvent, etc. can be cited. As the solvent, for example, the solvents (organic solvents) exemplified in the reaction of the compound represented by the formula (Ia) and the compound represented by the formula (Ib) or the above solvents can be used. The developer may contain a surfactant. As the development method, spin coating immersion method, dipping method, spraying method, etc. can be cited. It is also possible to further heat (post-baking) the patterned cured film (cured layer) obtained by development.

[0265] The cured product or the molded article containing it is formed from the composition, and thus can exhibit 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 of the cured product or the molded article containing it at a wavelength of 550 nm can be 1.600 or more, 1.650 or more, 1.670 or more, 1.680 or more, 1.690 or more, or 1.695 or more. The refractive index of the cured product or the molded article containing it at a wavelength of 550 nm is, for example, 2.000 or less, and can also be 1.900 or less.

[0266] The refractive index at a wavelength of 550 nm of the cured product or the molded product containing the same can be measured, for example, by the following method. First, a coating film is formed on a substrate, and the coating film is cured to obtain a substrate having a cured film formed thereon. Next, for the substrate having the cured film formed thereon, a Δψ spectrum is measured using an ellipsometer (manufactured by J.A. Woollam Co., "M-2000"), the refractive index dispersion is obtained using the attached analysis software, and the refractive index at a wavelength of 550 nm is obtained. Thus, the refractive index at a wavelength of 550 nm of the cured product or the molded product containing the same can be obtained.

[0267] <Use applications>

[0268] As applications of the cured product or the molded product, for example, glass substitutes and surface coating materials thereof can be cited; coating materials for window glass, daylighting glass, and light source protection glass for houses, facilities, transportation equipment, etc.; window films for houses, facilities, transportation equipment, etc.; interior and exterior decoration materials and interior and exterior decorative coatings for houses, facilities, transportation equipment, etc., and coating films formed using the coatings; alkyd resin spray paints and coating films formed using the paints; acrylic spray paints and coating films formed using the paints; components for light sources that emit ultraviolet rays such as fluorescent lamps and mercury lamps; materials for blocking electromagnetic waves generated from components for precision machinery, electronic and electrical equipment, and various displays; containers or packaging materials for foods, chemicals, pharmaceuticals, etc.; bottles, boxes, blister packs, cups, special packaging, laser disc coatings, agricultural and industrial sheets or films; anti-fading agents for printed matter, dyed matter, dyes, pigments, etc.; protective films for polymer supports (for example, for plastic parts of mechanical and automotive parts); printed matter protective layers; inkjet medium coatings; laminated light extinction materials; optical light films; safety glass / windshield interlayers; electrochromic / photochromic applications; over laminate films; solar heat control films; cosmetics such as sunscreen, shampoo, hair rinse, hair styling agents, etc.; fiber products and fibers for clothing such as sportswear, stockings, hats, etc.; interior household decorations such as curtains, carpets, wallpapers, etc.; medical appliances such as plastic lenses, contact lenses, artificial eyes, etc.; optical supplies such as optical filters, backlight display films, prisms, lenses (for example, spectacle lenses, camera lenses, and microlenses, pickup lenses, etc. described later), mirrors, photographic materials, etc.; stationery such as mold films, transfer stickers, anti-graffiti films, tapes, inks, etc.; signboards, indicators, etc. and their surface coating materials; substrates used in optical devices, etc.; optical waveguides; holograms; LED sealing materials, etc.

[0269] The molded article can be suitably used as an optical article, i.e., a lens, used in an optical device. Examples of the optical device include a solid-state imaging device, a display device, etc. In the solid-state imaging device, a lens for the purpose of improving the light condensing efficiency into each photoelectric conversion element can be used. Further, in the display device, a lens for the purpose of improving the light extraction efficiency from pixels can be used. The lens can be a microlens. Examples of the display device include a liquid crystal display device, an organic EL display device, etc.

[0270] As high refractive index materials, inorganic compounds such as zirconia and titanium oxide have been conventionally known. However, in the case of producing a molded article containing a high refractive index material formed of an inorganic compound, it is sometimes difficult to perform etching etc. and it is not easy to mold, and further, sometimes the high refractive index material scatters during molding and a contamination problem occurs. Such problems can be solved by using the high refractive index material of the present embodiment which is an organic compound.

[0271] Examples

[0272] Hereinafter, the present invention will be described more specifically by giving examples. However, the present invention is not limited to these examples. Note that hereinafter, unless otherwise specified, "parts" means "parts by mass".

[0273] [Synthesis Example 1]

[0274] <Synthesis of Compound (A-1)-1>

[0275]

[0276] The inside of a four-necked flask equipped with a Dimroth condenser and a thermometer was made into a nitrogen atmosphere, 10 parts of 1,6-naphthalenedithiol, 12.4 parts of 2-chloropropionic acid, 50 parts of acetone, 50 parts of pure water, and 10.4 parts of sodium hydroxide were added to the above flask, and the mixture was stirred at 25°C for 3 hours. The obtained mixture was purified to obtain 12.2 parts of a compound represented by the formula (A-1) (Compound (A-1)).

[0277] Perform 1 1H-NMR analysis and LC-MS measurement to confirm the formation of Compound (A-1).

[0278] 1 1H-NMR (deuterated chloroform) δ: 10.07 (2H), 8.40 to 8.43 (1H), 7.90 (1H), 7.72 to 7.74 (2H), 7.54 to 7.56 (1H), 7.34 to 737 (1H), 3.69 to 3.89 (2H), 1.47 to 1.51 (6H)

[0279] LC-MS: [M-H] + = 335.2

[0280] <Synthesis of Compound (A-1)-2>

[0281]

[0282] Using a method different from the above method, the compound represented by formula (A-1) (Compound (A-1)) was synthesized. The inside of a four-necked flask equipped with a Dimroth condenser and a thermometer was made into a nitrogen atmosphere, and 10 parts of 1,6-naphthalenedithiol, 12.4 parts of 2-chloropropionic acid, 33.6 parts of diisopropylethylamine, and 100 parts of toluene were added to the above flask, and the mixture was stirred at 100 °C for 3 hours. The obtained mixture was purified to obtain 15.4 parts of the compound represented by formula (A-1) (Compound (A-1)).

[0283] [Synthesis Example 2]

[0284] <Synthesis of Compound (A-2)>

[0285]

[0286] The inside of a four-necked flask equipped with a Dimroth condenser and a thermometer was made into a nitrogen atmosphere, and 5 parts of 1,6-naphthalenedithiol, 7 parts of 2-chlorobutyric acid, 50 parts of toluene, and 16.8 parts of diisopropylethylamine were added to the above flask, and the mixture was stirred at 110 °C for 3 hours. The obtained mixture was purified to obtain 5.8 parts of the compound represented by formula (A-2) (Compound (A-2)).

[0287] Perform 1 1H-NMR analysis and LC-MS measurement were carried out to confirm the formation of Compound (A-2).

[0288] 1 1H-NMR (deuterochloroform) δ: 8.00 - 9.00 (3H), 7.88 - 7.89 (1H), 7.56 - 7.73 (3H), 7.31 - 7.36 (1H), 3.52 - 3.67 (2H), 1.84 - 1.98 (4H), 1.05 - 1.12 (6H)

[0289] LC-MS: [M-H] + = 363.2

[0290] [Synthesis Example 3]

[0291] <Synthesis of Compound (A-3)>

[0292]

[0293] Make the atmosphere in a four-necked flask equipped with a Dimroth condenser and a thermometer a nitrogen atmosphere. Add 5 parts of 1,6-naphthalenedithiol, 9.8 parts of 3-chloro-2,2-dimethylpropanoic acid, 12.5 parts of acetone, 50 parts of pure water, and 5.2 parts of sodium hydroxide to the above flask, and stir at 75 °C for 3 hours. Purify the resulting mixture to obtain 10.1 parts of the compound represented by formula (A-3) (compound (A-3)).

[0294] Perform 1 H-NMR analysis and LC-MS measurement to confirm the formation of compound (A-3).

[0295] 1 H-NMR (deuterochloroform) δ: 8.38 - 8.40 (1H), 8.00 (1H), 7.80 - 7.82 (1H), 7.61 - 7.74 (2H), 7.41 - 7.45 (1H), 3.10 (4H), 1.26 - 1.28 (12H)

[0296] LC-MS: [M-H] + = 391.2

[0297] [Synthesis Example 4]

[0298] [Synthesis of Compound (A-4)]

[0299]

[0300] Make the atmosphere in a four-necked flask equipped with a Dimroth condenser and a thermometer a nitrogen atmosphere. Add 5 parts of 1,6-naphthalenedithiol, 7 parts of 3-chlorobutyric acid, 50 parts of toluene, and 16.8 parts of diisopropylethylamine to the above flask, and stir at 110 °C for 3 hours. Purify the resulting mixture to obtain 6.8 parts of the compound represented by formula (A-4) (compound (A-4)).

[0301] Perform 1 H-NMR analysis and LC-MS measurement to confirm the formation of compound (A-4).

[0302] 1 H-NMR (deuterochloroform) δ: 8.43 - 8,46 (1H), 7.94 - 7.96 (1H), 7.74 - 7.77 (2H), 7.60 - 7.63 (1H), 7.40 - 7.44 (1H), 3.57 - 3.85 (2H), 2.52 - 2.64 (4H), 1.39 - 1.42 (6H)

[0303] LC-MS: [M-H] + = 363.2

[0304] [Synthesis Example 5]

[0305] <Synthesis of Compound (A-5)>

[0306]

[0307] Make the inside of a four-necked flask equipped with a Dimroth condenser and a thermometer into a nitrogen atmosphere. Add 2.5 parts of 1,6-naphthalenedithiol, 4.3 parts of 2-chloro-3-methylvaleric acid, 25 parts of toluene, and 8.4 parts of diisopropylethylamine to the above flask, and stir at 25 °C for 3 hours. Purify the resulting mixture to obtain 5.2 parts of the compound represented by formula (A-5) (Compound (A-5)).

[0308] Perform 1 1H-NMR analysis and LC-MS measurement to confirm the formation of Compound (A-5).

[0309] 1 1H-NMR (chloroform-d) δ: 8.35 - 8.42 (1H), 7.86 - 7.91 (1H), 7.63 - 7.73 (4H), 7.33 - 7.36 (2H), 3.53 - 3.68 (2H), 1.87 - 2.09 (2H), 1.17 - 1.28 (4H), 0.91 - 1.10 (12H)

[0310] LC-MS: [M-H] + = 419.2

[0311] [Synthesis Example 6]

[0312] <Synthesis of Compound (A-6)>

[0313]

[0314] Make the inside of a four-necked flask equipped with a Dimroth condenser and a thermometer into a nitrogen atmosphere. Add 5 parts of 1,6-naphthalenedithiol, 8.6 parts of 2-chloro-4-methylvaleric acid, 50 parts of toluene, and 16.8 parts of diisopropylethylamine to the above flask, and stir at 25 °C for 3 hours. Purify the resulting mixture to obtain 8 parts of the compound represented by formula (A-6) (Compound (A-6)).

[0315] Perform 1 1H-NMR analysis and LC-MS measurement to confirm the formation of Compound (A-6).

[0316] 11H-NMR (CDCl₃) δ: 9.00 (2H), 8.40 - 8.43 (1H), 7.83 - 7.85 (1H), 7.71 - 7.73 (1H), 7.56 - 7.58 (2H), 7.30 - 7.33 (1H), 3.59 - 3.78 (2H), 1.64 - 1.85 (6H), 0.91 - 1.01 (12H)

[0317] LC-MS: [M-H] + = 419.2

[0318] [Synthesis Example 7]

[0319] [Synthesis of Compound (a-1)]

[0320]

[0321] According to the method described in International Publication No. 2023 / 058449, the compound represented by formula (a-1) (Compound (a-1)) was synthesized.

[0322] [Synthesis Example 8]

[0323] [Synthesis of Compound (B-1)]

[0324] ·Synthesis of Compound (B-1a)

[0325]

[0326] The inside of a four-necked flask equipped with a Dimroth condenser and a thermometer was made into 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 above flask, and the mixture was stirred in an ice bath for 15 minutes. Then, 15 parts of sodium hydroxide, 66 parts of acetone, and 203 parts of pure water were added to another flask, and after complete dissolution, it was added dropwise to the above 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 (B-1a) (Compound (B-1a)).

[0327] Perform 1 1H-NMR analysis and LC-MS measurement to confirm the formation of Compound (B-1a).

[0328] 1 1H-NMR (CDCl₃) 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)

[0329] LC-MS: [M+H] + = 305.5

[0330] · Synthesis of Compound (B-1)

[0331]

[0332] Make the inside of a four-necked flask equipped with a Dimroth condenser and a thermometer into a nitrogen atmosphere, and add 3 parts of compound (B-1a), 30 parts of methanol, 30 parts of toluene, 0.05 part of acetic anhydride, and 3.8 parts of thiourea to the above flask, and stir at room temperature for 24 hours. Purify the obtained mixture to obtain 2.5 parts of the compound represented by formula (B-1) (compound (B-1)).

[0333] Perform 1 1H-NMR analysis and LC-MS measurement to confirm the formation of compound (B-1).

[0334] 1 1H-NMR (deuterochloroform) 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)

[0335] LC-MS: [M+H] + = 337.5

[0336] [Examples 1 - 15 and Comparative Examples 1 - 3]

[0337] [Preparation of Composition]

[0338] Charge the compounding ingredients shown in Table 1 in the amounts shown in Table 1 (unit: parts by mass) into a flask, and stir to prepare the liquid compositions of Examples 1 - 15 and Comparative Examples 1 - 3. The compositions of Examples 1 - 15 and Comparative Examples 1 - 3 were transparent to the naked eye, and it was confirmed that the compounding ingredients were uniformly dissolved.

[0339] Details of the abbreviations of the compounding ingredients shown in Table 1 are as described below.

[0340] Component (A): Compound represented by formula (I)

[0341] · (A-1): Compound (A-1) synthesized in Synthesis Example 1

[0342] · (A-2): Compound (A-2) synthesized in Synthesis Example 2

[0343] ·(A-3): The compound (A-3) synthesized in Synthesis Example 3

[0344] ·(A-4): The compound (A-4) synthesized in Synthesis Example 4

[0345] ·(A-5): The compound (A-5) synthesized in Synthesis Example 5

[0346] ·(A-6): The compound (A-6) synthesized in Synthesis Example 6

[0347] (a) component: A carboxylic acid compound other than the (A) component

[0348] ·(a-1): The compound (a-1) synthesized in Synthesis Example 7

[0349] (B) component: A compound having a group represented by formula (X)

[0350] ·(B-1): The compound (B-1) synthesized in Synthesis Example 8

[0351] (C) component: A curing agent

[0352] ·(C-1): An aromatic sulfonium salt (manufactured by San-Apro Ltd., "VC-1FG")

[0353] ·(C-2): An aromatic sulfonium salt (manufactured by San-Apro Ltd., "VC-1S")

[0354] (D) component: An alicyclic epoxy compound

[0355] ·(D-1): A compound having a structure in which at least one alicyclic unsaturated hydrocarbon is epoxidized (manufactured by Daicel Corporation, "Celloxide 2021P")

[0356] ·(D-2): A compound having a structure in which at least one alicyclic unsaturated hydrocarbon is epoxidized (manufactured by Daicel Corporation, "Celloxide 8010")

[0357] ·(D-3): A compound having a structure in which at least one alicyclic unsaturated hydrocarbon is epoxidized (manufactured by Daicel Corporation, "Celloxide 2081")

[0358] ·(D-4): A compound having a structure in which at least one alicyclic unsaturated hydrocarbon is epoxidized (manufactured by Daicel Corporation, "Epolead GT401")

[0359] ·(D-5): A compound having a structure formed by epoxidizing at least one alicyclic unsaturated hydrocarbon (manufactured by ENEOS Corporation, "EPOCHALIC THI-DE")

[0360] Solvent

[0361] ·(E-1): PGMEA (propylene glycol monomethyl ether acetate)

[0362] [Table 1]

[0363]

[0364] <Evaluation Test> (1) Film-forming property

[0365] For the compositions of Examples 1 to 15 and Comparative Examples 1 to 3, a coating film was formed by the following method, and the film-forming property was evaluated. Approximately 3 mL of the composition was dropped onto an alkali-free glass plate (thickness: 0.7 mm, size: 50 mm × 50 mm, manufactured by Corning, "Eagle XG"), and spin-coated using a spin coater (manufactured by MIKASA Corporation, "MS-B100") under the conditions of 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.

[0366] 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 2. Note that an open-hole defect refers to a state in which a hole with a diameter of 1 mm or more is formed in the coating film and the alkali-free glass plate is exposed. A depression defect refers to the following state: Although no exposed portion of the alkali-free glass plate is observed, the local film thickness is locally thinned around environmental foreign matters or the like, and a pit-shaped defect with a diameter of less than 1 mm is generated. The results are shown in Table 2.

[0367] 5: Colorless and transparent, and neither open-hole defects nor depression defects are observed.

[0368] 4: Two or more and less than five depression defects are observed.

[0369] 3: Two or more and less than five open-hole defects are observed.

[0370] 2: Two or more and less than five open-hole defects and two or more and less than five depression defects are respectively observed.

[0371] 1: Five or more open-hole defects and five or more depression defects are respectively observed.

[0372] (2) Formation of cured film

[0373] About 3 mL of the compositions of Examples 1 to 15 and Comparative Examples 1 to 3 were respectively dropped onto the polished surface of a silicon wafer (with a thickness of 0.5 mm, a diameter of 4 inches, manufactured by Rokukai Electronics Co., Ltd.), and spin-coated at 1000 rpm for 20 seconds using a spin coater (manufactured by MIKASA Co., Ltd., "MS-B100") to form a coating film. The silicon wafer with the coating film formed thereon was heated at 60 °C for 2 minutes to remove the solvent. For the obtained coating film, on the silicon wafer with the cured film formed thereon, a high-pressure mercury lamp proximity UV exposure apparatus (manufactured by USHIO INC., "UV-3300SC") was used, and in an atmospheric atmosphere, proximity exposure was performed with an irradiation energy of 1000 mJ / cm 2 with a gap of 200 μm provided between the photomask and the coating surface through the photomask. For the obtained silicon wafer, as post-baking, it was heated at 120 °C for 10 minutes to obtain a silicon wafer with a cured film formed thereon. The film thickness of the cured film on the silicon wafer was measured using a stylus profilometer (manufactured by Bruker Corporation, "DekTak XT"). As a result, the film thickness was 1.5 μm for all.

[0374] (3) Solvent resistance (film thickness retention rate)

[0375] Using the silicon wafer with the cured film formed in the above (2), the solvent resistance (film thickness retention rate) of the cured film was evaluated according to the following evaluation criteria. For solvent resistance, the silicon wafer with the cured film formed thereon was immersed in acetone at 23 °C for 10 minutes, and evaluation was performed by observing the appearance change of the cured film before and after immersion and calculating the film thickness retention rate before and after immersion (film thickness retention rate = film thickness of the cured film after immersion / film thickness of the cured film before immersion). The results are shown in Table 2.

[0376] 5: The film thickness retention rate is 95% or more and 100% or less.

[0377] 4: The film thickness retention rate is 90% or more and less than 95%.

[0378] 3: The film thickness retention rate is 80% or more and less than 90%.

[0379] 2: The film thickness retention rate is 50% or more and less than 80%.

[0380] 1: The film thickness retention rate is less than 50%.

[0381] (4) Measurement of refractive index

[0382] For the silicon wafer with the cured film formed in the above (2), the Δψ spectrum was measured using an ellipsometer (manufactured by J.A. Woollam Co., Ltd., "M-2000"), the refractive index dispersion was obtained using the attached analysis software, and the refractive index at a wavelength of 550 nm was obtained. The results are shown in Table 2.

[0383] (5) Alkaline developability

[0384] Approximately 3 mL of the compositions of Examples 1 to 15 and Comparative Examples 1 to 3 were respectively dropped onto the polished surface of a silicon wafer (thickness: 0.5 mm, diameter: 4 inches, manufactured by Rokukai Electronics Co., Ltd.), and spin-coated using a spin coater (manufactured by MIKASA Co., Ltd., "MS-B100") under the conditions of 1000 rpm and 20 seconds to form a coating film. The silicon wafer with the coating film formed thereon was heated at 60 °C for 2 minutes to remove the solvent. Next, using a high-pressure mercury lamp proximity UV exposure apparatus (manufactured by USHIO INC., "UV-3300SC"), in an atmospheric atmosphere, with an irradiation energy of 1000 mJ / cm 2 , proximity exposure was performed through a photomask with a 200-μm gap provided between the photomask and the coating surface. Then, it was immersed in a 2.38 mass% aqueous solution of TMAH (tetramethylammonium hydroxide) for 1 minute and then in pure water for 1 minute for development. Next, it was heated on a hot plate at 120 °C for 5 minutes to obtain a silicon wafer having a patterned cured film formed thereon.

[0385] For the patterned cured film, the pattern formability was evaluated based on the following evaluation criteria. The results are shown in Table 2.

[0386] 5: The line width is less than 3 μm.

[0387] 4: The line width is 3 μm or more and less than 5 μm.

[0388] 3: The line width is 5 μm or more and less than 10 μm.

[0389] 2: The unexposed portion is completely insoluble in the developer and no pattern is formed.

[0390] 1: Both the exposed portion and the unexposed portion are completely dissolved in the developer and no pattern is formed.

[0391] For the patterned cured film with a pattern formability evaluation of 3 to 5, the film thickness difference between the exposed portion and the unexposed portion after development was measured, and the dissolution contrast was evaluated based on the following evaluation criteria. As reasons for the decrease in the dissolution contrast, insufficient dissolution of the unexposed portion, dissolution of the exposed portion, etc. can be cited. The results are shown in Table 2.

[0392] 5: The film thickness difference between the exposed portion and the unexposed portion after development is 1.3 μm or more and 1.5 μm or less.

[0393] 4: The film thickness difference between the exposed portion and the unexposed portion after development is 1.0 μm or more and less than 1.3 μm.

[0394] 3: The film thickness difference between the exposed portion and the unexposed portion after development is 0.5 μm or more and less than 1.0 μm.

[0395] 2: The film thickness difference between the exposed portion and the unexposed portion after development is 0.1 μm or more and less than 0.5 μm.

[0396] 1: The film thickness difference between the exposed portion and the unexposed portion after development is less than 0.1 μm.

[0397] [Table 2]

[0398]

[0399] As shown in Table 2, compared with the composition of the comparative example, the refractive index of the composition of the example is sufficiently high and the alkali developability is excellent. In addition, it was clarified that the film-forming property of the composition of the example is also excellent, and the solvent resistance (film thickness retention rate) of the cured product of the composition of the example is also excellent. From these results, it was confirmed that the composition of the present invention can provide a cured product having a high refractive index and excellent alkali developability.

Claims

1. A composition comprising a compound represented by formula (I), a compound having a group represented by formula (X), and a curing agent, In formula (I), L represents a branched alkylene group having 2 to 20 carbon atoms which may have a substituent, and the two Ls may be the same or different; A represents a hydrogen atom or a cation, and the two As may be the same or different; n represents an arbitrary integer from 0 to 6; R represents a monovalent substituent, and when there are a plurality of Rs, the plurality of Rs may be the same or different; In formula (X), Ring Z containing a sulfur atom as a constituent atom x represents a 3-membered ring or a 4-membered ring; R 2x represents a hydrogen atom or a monovalent substituent; * represents the bonding position.

2. The composition according to claim 1, wherein The compound represented by formula (I) is a compound represented by formula (I-1), In formula (I-1), A, n, and R have the same meanings as described above; m represents an arbitrary integer from 1 to 6; R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 1 and R 2 When there are multiple ones, multiple Rs 1 and R 2 may be the same or different; Among them, when m is 1, R 1 and R 2 at least one of them is an alkyl group having 1 to 6 carbon atoms. When m is 2 or more, there are multiple R 1 and R 2 at least one of them is an alkyl group having 1 to 6 carbon atoms.

3. The composition according to claim 1, wherein The curing agent contains a photoacid generator.

4. The composition according to claim 1, wherein, The compound having a group represented by formula (X) contains a compound represented by formula (II), In formula (II), L 1x represents a single bond or a divalent group, and there are two Ls 1x which may be the same or different; A 1x represents an oxygen atom or a sulfur atom, and there are two A's 1x which may be the same or different; among them, at least one of the two A's 1x is a sulfur atom; mx represents 0 or 1, and the two mx may be the same or different; nx represents an arbitrary integer from 0 to 6; R 1x represents a monovalent substituent, R 1x When there are multiple ones, there are multiple Rs 1x which may be the same or different; R 2x represents a hydrogen atom or a monovalent substituent, and there are two Rs 2x which may be the same or different.

5. The composition according to claim 1, further comprising an alicyclic epoxy compound.

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

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

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

9. A solid-state imaging device comprising the cured product according to claim 7.

10. A compound represented by formula (I), In formula (I), L represents a branched alkylene group having 2 to 20 carbon atoms which may have a substituent, and the two Ls may be the same or different; A represents a hydrogen atom or a cation, and the two As may be the same or different; n represents an arbitrary integer from 0 to 6; R represents a monovalent substituent, and when there are a plurality of Rs, the plurality of Rs may be the same or different.

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