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 capable of providing a cured product exhibiting a high refractive index and excellent solvent resistance. The solution of the present invention is a composition containing: a compound having at least one thiirane group or thietanyl group; an alicyclic epoxy compound having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized; a photoacid generator; and a compound having a group represented by formula (Z). In formula (Z), A represents a hydrogen atom or a cation. 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 the 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. 2011 / 102258 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] The main object of the present invention is to provide a composition capable of providing a cured product exhibiting a high refractive index and excellent solvent resistance.

[0008] Means for Solving the Problems

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

[0010] [1] A composition comprising:

[0011] a compound having at least one thiiranyl or thietanyl group;

[0012] an alicyclic epoxy compound having a structure obtained by epoxidizing an alicyclic unsaturated hydrocarbon;

[0013] a photoacid generator; and

[0014] a compound having a group represented by formula (Z).

[0015]

[0016] [In formula (Z),

[0017] A represents a hydrogen atom or a cation.

[0018] * represents a bonding position. ]

[0019] [2] The composition according to [1], wherein the compound having at least one thiiranyl or thietanyl group comprises a compound represented by formula (II).

[0020]

[0021] [In formula (II),

[0022] L 1x represents a single bond or a divalent group, and two Ls 1x may be the same or different.

[0023] A 1x represents an oxygen atom or a sulfur atom, and two As 1x may be the same or different. Among them, at least one of the two As 1x is a sulfur atom.

[0024] mx represents 0 or 1, and two mx's

[0025] may be the same or different.

[0026] R 1x represents a monovalent substituent, and when there are multiple Rs 1x (in the case of multiple existences), multiple Rs 1x may be the same or different.

[0027] R 2x represents a hydrogen atom or a monovalent substituent, and two Rs 2x may be the same or different.]

[0028] [3] The composition according to [1], wherein the alicyclic epoxide having a structure formed by epoxidation of an alicyclic unsaturated hydrocarbon is a compound having at least two structures formed by epoxidation of alicyclic unsaturated hydrocarbons in one molecule.

[0029] [4] The composition according to [1], wherein the compound having a group represented by formula (Z) comprises a compound represented by formula (I).

[0030]

[0031] [In formula (I),

[0032] L represents a branched alkylene group having 2 to 20 carbon atoms which may have substituents, and two Ls

[0033] may be the same or different.

[0034] n represents any integer from 0 to 6.

[0035] R represents a monovalent substituent, and when there are multiple Rs, the multiple Rs may be the same or different.

[0036] [5] A molded article formed by curing the composition according to any one of [1] to [4].

[0037] [6] A cured product of the composition according to any one of [1] to [4].

[0038] [7] A display device comprising the cured product according to [6].

[0039] [8] A solid-state imaging device comprising the cured product according to [6].

[0040] Advantages of the Invention

[0041] According to the present invention, a composition capable of providing a cured product exhibiting a high refractive index and excellent solvent resistance can be provided. In addition, according to the present invention, a composition having excellent alkali developability even without pre-baking before development can be provided. The film-forming property and the like of the composition in some embodiments are also excellent. Further, according to the present invention, a molded article using such a composition, a cured product of such a composition, a display device comprising the cured product, and a solid-state imaging device comprising the cured product can be provided. Detailed Embodiments

[0042] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0043] In this specification, a numerical range indicated by "~" represents a range including the 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 of 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.

[0044] In this specification, (meth)acrylate refers to acrylate or its corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl and (meth)acrylate.

[0045] In this specification, for the materials exemplified below, unless otherwise specified, within the scope that meets the conditions, one kind can be used alone, or two or more kinds can be used in combination. Regarding the content of each component, when there are multiple substances belonging to each component, unless otherwise specified, it refers to the total amount of the multiple substances.

[0046] <Composition>

[0047] The composition of one embodiment contains: a compound having at least one thiiranyl or thietanyl group (hereinafter, sometimes referred to as “component (A)”), an alicyclic epoxy compound having a structure formed by epoxidizing an alicyclic unsaturated hydrocarbon (hereinafter, sometimes referred to as “component (B)”), a photoacid generator (hereinafter, sometimes referred to as “component (C)”), and a compound having a group represented by formula (Z) (hereinafter, sometimes referred to as “component (D)”). According to the composition of the present embodiment, a cured product having a high refractive index and excellent solvent resistance can be provided. The composition of the present embodiment can be suitably used, for example, as a negative resist.

[0048] Component (A): A compound having at least one thiiranyl or thietanyl group

[0049] The composition of the present embodiment contains component (A). Component (A) may be a curable compound. By including component (A) in the composition, component (A) itself polymerizes, or both component (A) and component (B) polymerize, thereby enabling the provision of a cured product having a high refractive index. The cured product of the composition containing component (A) tends to have excellent solvent resistance.

[0050] Lithography is the following method: A composition is coated on a substrate, dried as needed to form a coating film (coating layer), and the coating film is exposed through a photomask, thereby curing the exposed portion, and the exposed coating film is developed (removing the unexposed portion). 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 component (A), there is a tendency that a patterned cured film can be easily obtained by development even without pre-development baking. Therefore, by including component (A) in the composition, the step of pre-development baking can be omitted in the processes of exposure and development, and the productivity of the molded product can be improved.

[0051] Component (A) can be used without particular limitation as long as it is a compound having at least one thiiranyl or thietanyl group. Component (A) can be, for example, a compound having at least one group represented by formula (II-a), and preferably a compound having at least one group represented by formula (II-b).

[0052]

[0053] In formula (II-a),

[0054] mx represents 0 or 1.

[0055] R 2x represents a hydrogen atom or a monovalent substituent.

[0056] * represents the bonding position.

[0057]

[0058] In formula (II-b),

[0059] L 1x represents a single bond or a divalent group.

[0060] mx represents 0 or 1.

[0061] R 2x represents a hydrogen atom or a monovalent substituent.

[0062] * represents the bonding position.

[0063] As the divalent group represented by L 1x for example, there may be mentioned 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 replaced by -O-, -S-, -NR A -(R A represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.). -CO-, or -SO2-.

[0064] As the divalent aliphatic chain hydrocarbon group, for example, there may be mentioned a saturated or unsaturated aliphatic chain hydrocarbon group. More specifically, there may be mentioned alkane diyl groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, octadecane-1,18-diyl, nonadecane-1,19-diyl, eicosane-1,20-diyl, etc. The divalent aliphatic chain hydrocarbon group may 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, still more preferably 1 to 4, and particularly preferably 1 or 2.

[0065] As the substituents which the divalent aliphatic chain hydrocarbon group may have, for example, there may be mentioned halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0066] As the divalent alicyclic hydrocarbon group, for example, a saturated or unsaturated alicyclic hydrocarbon group can be mentioned. More specifically, monocyclic alicyclic hydrocarbon groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cyclooctanediyl, cyclononanediyl, cyclodecanediyl, etc.; 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. are exemplified. 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.

[0067] As substituents that the divalent 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.; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0068] The divalent aromatic hydrocarbon group may be monocyclic or polycyclic. As the divalent aromatic hydrocarbon group, for example, phenylene, naphthylene, anthracenediyl, fluorenediyl, etc. are exemplified. The number of carbon atoms of the divalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0069] As substituents that the divalent 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.; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0070] As the monovalent substituent represented by R 2x For example, 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 (for example, aralkyl), etc. monovalent hydrocarbon groups; hydroxyl group; amino group, monomethylamino, monoethylamino, dimethylamino, diethylamino, methylethylamino, etc. amino groups which may be substituted by one or two alkyl groups having 1 to 6 carbon atoms; aliphatic heterocyclic groups having 4 to 20 carbon atoms or aromatic heterocyclic groups having 3 to 20 carbon atoms such as pyrrolidinyl, pyrroline, imidazolidinyl, imidazoline, oxazoline, thiazole, piperidinyl, morpholinyl, piperazinyl, indole, isoindole, quinoline, thiophene, pyrrole, furan, etc. heterocyclic groups; halogen atoms; nitro group; cyano group; carboxyl group; sulfo group; mercapto group; formyl group; -SF3 group; -SF5 group. The methylene (-CH2-) contained in the monovalent substituent may be replaced by -O-, -S-, -NRB -(R B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)., -CO-, or -SO2-. It should be noted that, as a group obtained by replacing the methylene group (-CH2-) contained in the monovalent substituent with -O-, examples 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.

[0071] As the monovalent aliphatic chain hydrocarbon group, for example, a saturated or unsaturated aliphatic chain hydrocarbon group can be cited. 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, etc. The monovalent aliphatic chain hydrocarbon group can 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, further preferably 1 to 4, and particularly preferably 1 or 2.

[0072] As substituents that the monovalent aliphatic chain hydrocarbon group may have, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydroxyl group; amino group; acetyl group; cyano group, etc. can be cited.

[0073] As the monovalent alicyclic hydrocarbon group, for example, a saturated or unsaturated alicyclic hydrocarbon group can be cited. More specifically, examples include monocyclic alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, cyclodecyl; 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. 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, further preferably 5 or 6.

[0074] As substituents that the monovalent alicyclic hydrocarbon group may have, for example, alkyl groups having 1 to 10 (preferably 1 to 4 carbon atoms) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydroxyl group; amino group; acetyl group; cyano group, etc. can be cited.

[0075] 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.

[0076] Examples of the substituent that the monovalent aromatic hydrocarbon group may have include alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; hydroxyl group; amino group; acetyl group; and cyano group.

[0077] mx represents 0 or 1. When mx is 0, it represents a three-membered ring structure of thiiranyl, and when mx is 1, it represents a four-membered ring structure of thietanyl. mx is preferably 0.

[0078] From the viewpoint of the high refractive index of the cured product, the component (A) is preferably a compound containing an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring; and 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, more preferably a naphthalene ring.

[0079] From the viewpoint of the high refractive index of the cured product, the component (A) is preferably a compound represented by the formula (II).

[0080]

[0081] In the formula (II),

[0082] L 1x represents a single bond or a divalent group, and two Ls 1x may be the same or different.

[0083] A 1x represents an oxygen atom or a sulfur atom, and two As 1x may be the same or different. Among them, at least one of the two As 1x is a sulfur atom.

[0084] mx represents 0 or 1, and two mx's

[0085] nx represents any integer from 0 to 6.

[0086] R 1x represents a monovalent substituent, and when there are a plurality of Rs 1x the plurality of Rs 1x may be the same or different.

[0087] R 2x represents a hydrogen atom or a monovalent substituent, and two Rs 2x may be the same or different.

[0088] In the compound represented by formula (II), two groups represented by formula (II-c) may be bonded to any position of the 1-8 positions of the naphthalene ring. The group 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 group represented by formula (II-c) on the naphthalene ring is 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).

[0089]

[0090] In formula (X), L 1x , A 1x , mx, and R 2x have the same meanings as described above, and * represents the bonding position.

[0091] When the compound represented by formula (II) has one or more monovalent substituents represented by R 1x , the monovalent substituent represented by R 1x may 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 (II-c).

[0092] L 1x represents a single bond or a divalent group, and two L 1x may be the same or different. In the compound represented by formula (II), 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 1-10, more preferably 1-6, further preferably 1-4, and particularly preferably 1 or 2.

[0093] A 1x represents an oxygen atom or a sulfur atom, and two A 1x may be the same or different. Among them, at least one of the two A 1x is a sulfur atom. In the compound represented by formula (II), for the two A 1x , both are preferably sulfur atoms. As the number of sulfur atoms as A 1x increases, there is a tendency to be able to supply a cured product having a higher refractive index and more excellent solvent resistance.

[0094] mx represents 0 or 1, and 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.

[0095] nx represents an integer of 0 to 6. nx is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 0.

[0096] R 1x represents a monovalent substituent, R 1x There are multiple cases where there are multiple R 1x They can be the same or different. 1x The monovalent substituent represented by R can be exemplified by 2x The monovalent substituent represented by is the same as the substituent.

[0097] R 2x represents a hydrogen atom or a monovalent substituent, and there are two R 2x In the compound represented by formula (II), there are two R 2x It is preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group, more preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group having 1 to 6 carbon atoms, further preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

[0098] Examples of component (A) (compound represented by formula (II)) include compounds represented by formula (II-A), formula (II-B), formula (II-C), formula (II-D), formula (II-E), and formula (II-F). L in formula (II-A), formula (II-B), formula (II-C), formula (II-D), formula (II-E), and formula (II-F) 1x , A 1x 、mx、nx、R 1x , and R 2x Means the same as above.

[0099]

[0100] In formula (II-A), formula (II-B), formula (II-C), formula (II-D), formula (II-E), and formula (II-F), there are two L 1x In this case, the number of carbon atoms in the alkanediyl group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 or 2.

[0101] In Formula (II-A), Formula (II-B), Formula (II-C), Formula (II-D), Formula (II-E), and Formula (II-F), two of the mx's are each independently 0 or 1, preferably 0. In Formula (II-A), Formula (II-B), Formula (II-C), Formula (II-D), Formula (II-E), and Formula (II-F), preferably, both of the two mx's are 0.

[0102] In Formula (II-A), Formula (II-B), Formula (II-C), Formula (II-D), Formula (II-E), and 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.

[0103] In Formula (II-A), Formula (II-B), Formula (II-C), Formula (II-D), Formula (II-E), and Formula (II-F), two of the A's 1x are each independently an oxygen atom or a sulfur atom. Among them, at least one of the two A's 1x is a sulfur atom. The A's 1x are preferably both sulfur atoms.

[0104] In Formula (II-A), Formula (II-B), Formula (II-C), Formula (II-D), Formula (II-E), and Formula (II-F), two of the R's 2x are each independently preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group, more preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group having 1 to 6 carbon atoms, 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. The two R's 2x are preferably the same.

[0105] Specific examples of the component (A) (the compound represented by Formula (II)) are shown below, but are not limited thereto.

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113] From the viewpoint of synthesis, the molecular weight of component (A) 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 component (A) is preferably 50 or more, more preferably 100 or more, and still more preferably 150 or more.

[0114] The compound represented by formula (II) as component (A) can be obtained by synthesizing the compound represented by formula (II-1) and reacting the compound represented by formula (II-1) with a sulfurizing agent.

[0115]

[0116] In formula (II-1), L 1x , mx, nx, R 1x , and R 2x represent the same meanings as described above (formula (I)).

[0117] The compound represented by formula (II-1) can be obtained, for example, by a method including a step of reacting the compound represented by formula (II-1a) with the compound represented by formula (II-1b).

[0118]

[0119] In formula (II-1a), nx and R 1x represent the same meanings as described above.

[0120]

[0121] In formula (II-1b), L 1x , mx, and R 2x represent the same meanings as described above, and X 1X represents a leaving group.

[0122] The reaction of the compound represented by formula (II-1a) with the compound represented by formula (II-1b) can be carried out, for example, in the presence of a base. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium hydride, lithium aluminum hydride, sodium borohydride, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate; metal alkoxides such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium tert-butoxide, potassium tert-butoxide; 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, tetramethylammonium chloride. 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 still more preferably 0.1 to 3 moles, relative to 1 mole of the compound represented by formula (II-1a).

[0123] In addition, two or more kinds of bases can 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 bicarbonate and metal hydroxide is more preferred. In the case of using in combination, the two can be added simultaneously or added stepwise.

[0124] In the compound represented by formula (II-1b), as the leaving group represented by X 1X Examples include halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; 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. Specific examples of the compound represented by formula (II-1b) include epihalohydrin compounds (L 1x is methylene, mx is 0, R 2x is a hydrogen atom and X is a halogen atom). The amount of the compound represented by formula (II-1b) used can be, for example, 0.01 to 20 moles, preferably 0.5 to 15 moles, relative to 1 mole of the compound represented by formula (II-1a). In this step, the reaction can also be carried out using two or more kinds of the compounds represented by formula (II-1b).

[0125] The reaction of the compound represented by formula (II-1a) with the compound represented by formula (II-1b) is preferably carried out in a solvent. As the solvent, in addition to water, organic solvents such as ketones, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, alcohols, glycol dimethyl ethers, esters, aliphatic nitriles, sulfoxides, amides, etc. can be cited. The following solvents can be exemplified as the organic solvents.

[0126] Ketones: acetone, methyl ethyl ketone, diethyl ketone, butyl methyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, 2-heptanone, 2-octanone, cyclopentanone, cyclohexanone, etc.

[0127] Aromatic hydrocarbons: benzene, toluene, xylene, mesitylene, naphthalene, anisole, nitrobenzene, aniline, tetralin, durene, etc.

[0128] Halogenated aromatic hydrocarbons: chlorobenzene, dichlorobenzene, chloronaphthalene, etc.

[0129] Aliphatic hydrocarbons: pentane, hexane, heptane, etc.

[0130] Halogenated aliphatic hydrocarbons: dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, tetrachloroethylene, etc.

[0131] Ethers: diethyl ether, diisopropyl ether, methyl tert-butyl ether, cyclopentyl methyl ether, diphenyl ether, dimethoxyethane, dioxane, etc.

[0132] Alcohols: methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, hexafluoroisopropanol, etc.

[0133] Glycol dimethyl ethers: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, diethylene glycol butyl methyl ether, etc.

[0134] Esters: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc.

[0135] Aliphatic nitriles: acetonitrile, etc.

[0136] Sulfoxides: dimethyl sulfoxide, sulfolane, etc.

[0137] Amides: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0138] The temperature of the reaction of the compound represented by formula (II-1a) with the compound represented by 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.

[0139] By operating as described above, the compound represented by formula (II-1) can be obtained. When the obtained compound represented by formula (II-1) is used in the synthesis of the compound represented by formula (II), the compound represented by formula (II-1) can be used after separation or directly without separation.

[0140] The compound represented by formula (II) can be obtained, for example, by a method including a step of reacting the compound represented by formula (II-1) with a sulfurizing agent.

[0141] The reaction of the compound represented by formula (II-1) with a sulfurizing agent is a reaction in which the oxygen atom of the epoxy ring or oxetanyl ring possessed by the compound represented by formula (II-1) is replaced with a sulfur atom using the sulfurizing agent to form a thiirane ring (episulfide ring) or a thietane ring. Examples of 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. With respect to 1 mol of the compound represented by formula (II-1), the amount of the sulfurizing agent used is, for example, 0.01 to 20 mol, preferably 0.5 to 10 mol. 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 formula (II-1) can be replaced with sulfur atoms, or one oxygen atom in the compound represented by formula (II-1) can be replaced with a sulfur atom.

[0142] The reaction of the compound represented by formula (II-1) with a sulfurizing agent is preferably carried out in a solvent. Examples of the solvent include 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). 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.

[0143] In order to inhibit the polymerization of the generated compound represented by formula (II), a polymerization inhibitor can be added to the reaction system. Examples of the polymerization inhibitor include acids, acid anhydrides, etc. More specifically, examples include:

[0144] Inorganic acidic compounds such as nitric acid, hydrogen chloride (hydrochloric acid), perchloric acid, hypochlorous acid, chlorine dioxide, hydrofluoric acid, sulfuric acid, fuming sulfuric acid, sulfuryl chloride, boric acid, arsenic acid, arsenous acid, 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 pentoxide acid, 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;

[0145] 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;

[0146] 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 phosphites obtained by converting the phosphate moiety of them into phosphite moieties;

[0147] Organophosphorus compounds such as dialkyl dithiophosphoric acids represented by dimethyl dithiophosphoric acid;

[0148] Phenols such as phenol, catechol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl ethylphenol, resorcinol, hydroquinone, phloroglucinol, pyrogallol, cresol, ethylphenol, butylphenol, nonylphenol, hydroxyphenylacetic acid, hydroxyphenylpropionic acid, hydroxyphenylacetamide, methyl hydroxyphenylacetate, ethyl hydroxyphenylacetate, hydroxyphenylethanol, hydroxyphenylethylamine, hydroxyphenylaldehyde, phenylphenol, bisphenol-A, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bisphenol-F, bisphenol-S, α-naphthol, β-naphthol, aminophenol, chlorophenol, 2,4,6-trichlorophenol;

[0149] Methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, p-toluenesulfonic acid, ethylbenzenesulfonic acid, butylbenzenesulfonic acid, dodecylbenzenesulfonic acid, p-phenolsulfonic acid, o-cresolsulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 4B acid, diaminostilbenesulfonic acid, biphenylsulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, peri acid, laurenic acid, phenyl J acid and other sulfonic acids, etc.

[0150] 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 salt, or alkali metal dihydrogen phosphate salt.

[0151] For the product solution after the reaction, by washing with an acidic aqueous solution, the time-dependent stability 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 the polymerization inhibitor, etc. This acid can be used alone or in combination of two or more. There is a tendency that the acidic aqueous solution generally exhibits 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.

[0152] 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 Chemical Industry Co., Ltd.), NIONON 202A (an iron oxide-based adsorbent, manufactured by Ichikawa Shoji 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.

[0153] 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 (A) can be, for example, 10 to 90% by mass. Based on the total amount of the composition, the content of component (A) 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.

[0154] The total amount of the solid components of the composition refers to the sum of the components other than the solvent in the components contained in the composition. 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.

[0155] (B) Component: An alicyclic epoxy compound having a structure formed by epoxidizing an alicyclic unsaturated hydrocarbon

[0156] The composition of this embodiment contains the (B) component. The (B) component may be a curable compound. By making the composition contain the (B) component, there is a tendency for the solvent resistance of the cured product to be excellent.

[0157] (B) The component can be used without particular limitation as long as it is a compound having a structure formed by epoxidizing at least one alicyclic unsaturated hydrocarbon. 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. The (B) component is preferably a compound having at least two (more than 2) structures formed by epoxidizing alicyclic unsaturated hydrocarbons in one molecule. The number of structures formed by epoxidizing alicyclic unsaturated hydrocarbons in one molecule 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).

[0158] As specific examples of the (B) component, for example, Celloxide 2021P, Celloxide 8010, Celloxide 2081, Celloxide 2000, Epolead GT401, Cyclomer M100 (all manufactured by Daicel Corporation), EPOCHALIC (Japanese "エポカリック") THI-DE, EPOCHALIC DE-102, EPOCHALIC DE-103 (all manufactured by ENEOS Corporation) can be cited. Among them, the (B) component is preferably Celloxide 2021P, Celloxide 8010, Celloxide 2081, Epolead GT401, EPOCHALIC THI-DE, EPOCHALIC DE-102, or EPOCHALIC DE-103, which are compounds having at least two structures formed by epoxidizing alicyclic unsaturated hydrocarbons in one molecule, and more preferably Celloxide 2021P, Celloxide 8010, Celloxide 2081, or EPOCHALIC THI-DE.

[0159] The molecular weight of component (B) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, and particularly preferably 500 or less. The molecular weight of component (B) is preferably 50 or more, more preferably 100 or more, and still more preferably 150 or more.

[0160] 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, 1 to 30% by mass. Based on the total amount of the composition, the content of component (B) 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.

[0161] (C) Component: Photoacid generator

[0162] The composition of the present embodiment contains component (C). Component (C) is a compound that generates an acid upon irradiation with actinic energy rays to cause cationic polymerization of component (A) and / or component (B). Component (C) is also referred to as a photo cationic polymerization initiator.

[0163] Examples of component (C) include aromatic diazonium salts, aromatic sulfonium salts, aliphatic sulfonium salts, aromatic iodonium salts, pyridinium salts, cyclopentadienyliron(II) complexes, etc. When the photoacid generator is a sulfonium salt, examples of the counter anion include hexafluoroantimonate, hexafluorophosphate, P(F) x (Rf) 6-x - (wherein Rf represents a perfluoroalkyl group. x represents an integer of 1 to 5.), tetrafluoroborate, tetrakis(pentafluorophenyl)borate, etc.

[0164] Regarding the content of component (C), based on 100 parts by mass of the total amount of components (A) and (B), 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, still more preferably 1.0 part by mass or more, and from the viewpoints of making the alkali developability and / or heat resistance good, it is preferably 10 parts by mass or less, more preferably 9 parts by mass or less, and still more preferably 8 parts by mass or less.

[0165] (D) Component: A compound having a group represented by formula (Z)

[0166] The composition of the present embodiment contains component (D). By further containing component (D) in the composition, excellent alkali developability can be imparted to the resulting composition. Although the reason for obtaining such an effect is not necessarily clear, it is considered that in the exposure and development process of lithography, component (D) contributes to the removal of the unreacted composition.

[0167]

[0168] In formula (Z),

[0169] A represents a hydrogen atom or a cation.

[0170] * represents a bonding position.

[0171] 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, 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, for example, the bonds shown below within or between molecules.

[0172]

[0173] A represents a divalent cation. * represents a bonding position.

[0174] The group represented by formula (Z) is preferably the group represented by formula (Z-1).

[0175]

[0176] In formula (Z-1),

[0177] L represents a branched alkylene having 2 to 20 carbon atoms which may have substituents.

[0178] A has the same meaning as described above.

[0179] * represents a bonding position.

[0180] Examples of the branched alkylene 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 including the carbon atoms of the substituents is 2 to 20, preferably 2 to 10, more preferably 2 to 7, and further preferably 2 to 5.

[0181] Examples of the substituents that the branched alkylene may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; monovalent aromatic hydrocarbon groups such as phenyl group, naphthyl group, hydroxyl group; amino group; acetyl group; cyano group, etc.

[0182] (D) component preferably contains the compound represented by formula (I). By making the (D) component contain the compound represented by formula (I), the alkali developability of the resulting composition can be further improved.

[0183]

[0184] In formula (I),

[0185] L represents a branched alkylene group having 2 to 20 carbon atoms which may have substituents, and the two Ls may be the same or different.

[0186] A represents a hydrogen atom or a cation, and the two As may be the same or different.

[0187] n represents an arbitrary integer from 0 to 6.

[0188] R represents a monovalent substituent, and when there are a plurality of Rs, the plurality of Rs may be the same or different.

[0189] 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. For example, the groups represented by formula (Z-1) on the naphthalene ring may be bonded to any two positions of the 1st to 4th positions (5th to 8th positions), or may 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 groups represented by formula (Z-1) on the naphthalene ring are 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).

[0190] When the compound represented by formula (I) has one or more monovalent substituents represented by R, the monovalent substituents represented by R may be bonded to any position of the 1st to 8th positions of the naphthalene ring other than the bonding positions of the groups represented by formula (Z-1).

[0191] Examples of the monovalent substituent represented by R may be the same substituents as those represented by R 2x represented monovalent substituents.

[0192] (D) component preferably contains the compound represented by formula (I-1).

[0193]

[0194] In formula (I-1),

[0195] A, n, and R represent the same meanings as described above.

[0196] m represents an arbitrary integer from 1 to 6.

[0197] R 1 and R 2Each 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, the multiple Rs 1 and R 2 may be the same or different.

[0198] 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. When m is 2 or more, at least one of the multiple Rs 1 and R 2 is an alkyl group having 1 to 6 carbon atoms.

[0199] In the compound represented by formula (I-1), the two groups represented by formula (I-1-0) can be bonded to any position of the 1 to 8 positions of the naphthalene ring. The groups represented by formula (I-1-0) on the naphthalene ring can, for example, be bonded to any two positions of the 1 to 4 positions (5 to 8 positions), or can be bonded to any one position of the 1 to 4 positions (5 to 8 positions) and any one position of the 5 to 8 positions (1 to 4 positions). The groups represented by formula (I-1-0) on the naphthalene ring are preferably bonded to any one position of the 1 to 4 positions (5 to 8 positions) and any one position of the 5 to 8 positions (1 to 4 positions).

[0200]

[0201] In formula (I-1-0), A, m, R 1 , and R 2 represent the same meanings as described above. * represents the bonding position.

[0202] When the compound represented by formula (I-1) has one or more monovalent substituents represented by R, the monovalent substituents represented by R can be bonded to any position of the 1 to 8 positions of the naphthalene ring other than the bonding positions of the groups represented by formula (I-1-0).

[0203] m is preferably any integer from 1 to 4, more preferably any integer from 1 to 3, and still more preferably 1 or 2.

[0204] As the alkyl groups represented by R 1 and R 2 For example, methyl, ethyl, linear or branched propyl, linear or branched butyl, linear or branched pentyl, and linear or branched hexyl can be mentioned. The alkyl group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 2 carbon atoms.

[0205] When m is 1, R 1 and R 2At least one of them is an alkyl group having 1 to 6 carbon atoms. When m is 2 or more, there are multiple 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. The group represented by -[C(R 1 )(R 2 )]m- preferably has 2 to 10 carbon atoms including the carbon atoms of the substituents, more preferably 2 to 7 carbon atoms, and still more preferably 2 to 5 carbon atoms. The two groups represented by -[C(R 1 )(R 2 )]m- may be the same or different.

[0206] Specific examples of the component (D) are shown below, but are not limited thereto.

[0207]

[0208]

[0209]

[0210] From the viewpoint of synthesis, the molecular weight of the component (D) 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 (D) is preferably 200 or more, more preferably 250 or more, and still more preferably 300 or more.

[0211] The component (D) (the compound represented by the formula (I)) can be obtained, for example, by reacting the compound represented by the formula (Ia) (naphthalenedithiol) with the compound represented by the formula (Ib) (a carboxylic acid having a haloalkyl group) in the presence of a base.

[0212]

[0213] n and R have the same meanings as described above.

[0214]

[0215] L and A have 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.

[0216] As the base, the same bases as those used in the reaction of the compound represented by the formula (II-1a) and the compound represented by the formula (II-1b) can be exemplified. With respect to 1 mol of the compound represented by the formula (Ia), the amount of the base used can be, for example, 0.0001 to 10 mol, preferably 0.001 to 5 mol, more preferably 0.01 to 4 mol, and further preferably 0.1 to 3 mol.

[0217] With respect to 1 mol of the compound represented by the formula (Ia), the amount of the compound represented by the formula (Ib) used can be, for example, 0.01 to 20 mol, preferably 0.5 to 15 mol. In this step, the reaction can also be carried out using two or more compounds represented by the formula (Ib).

[0218] The reaction of the compound represented by the formula (Ia) and the compound represented by the formula (Ib) is preferably carried out in a solvent. As the solvent, the same solvents as those used in the reaction of the compound represented by the formula (II-1a) and the compound represented by the formula (II-1b) can be exemplified.

[0219] The reaction temperature of the compound represented by the formula (Ia) and the compound represented by the 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.

[0220] By operating as described above, the component (D) (the compound represented by the formula (I)) can be obtained. When using the component (D), the component (D) can be used after separation or can be used directly without separation.

[0221] From the viewpoint of easily obtaining the effects of the present invention sufficiently, the content of the component (D) can be, for example, 10 to 70% by mass based on the total amount of the solid components of the composition. Based on the total amount of the composition, the content of the component (D) 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.

[0222] As other components contained in the composition, for example, resins, curable compounds other than the components (A) and (B), solvents, additives, etc. can be cited. As additives, for example, polymerization inhibitors, inorganic particles, fillers, polymerization initiation aids, sensitizers, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, ultraviolet absorbers, antioxidants, dispersants, etc. can be cited.

[0223] (Resin)

[0224] The composition may contain one or more than two resins. By including a resin in the composition, 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. Examples of the resin include thermoplastic resins and curable resins. The curable resin may be a photocurable resin that is cured by irradiation with active energy rays, or a thermosetting resin that is cured by heat.

[0225] Examples of the thermoplastic resin include olefin resins such as polyethylene resin, polypropylene resin, and polycycloolefin resin; (meth)acrylic resins such as poly(meth)acrylate resin; styrene resins such as polystyrene resin, styrene-acrylonitrile resin, and acrylonitrile-butadiene-styrene resin; vinyl resins such as polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polyvinyl butyral resin, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol resin; polyester resins such as polyethylene terephthalate resin, polybutylene terephthalate resin, and liquid crystal polyester resin; polyacetal resin; polyamide resin; polycarbonate resin; polyurethane resin; and polyphenylene sulfide resin. One or more of these resins may be used as a polymer blend or polymer alloy.

[0226] Examples of the curable resin include resins having a photopolymerizable group or a thermopolymerizable group. More specifically, for example, (meth)acrylic resins, epoxy resins, melamine resins, unsaturated polyester resins, phenolic resins, urea resins, alkyd resins, and polyimide resins can be mentioned.

[0227] Other examples of the resin include alkali-soluble resins. By including an alkali-soluble resin in the composition, developability can be further imparted to the cured product of the composition. An 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 mentioned.

[0228] From the viewpoint of improving the developability and solvent resistance of the cured product of the composition, the acid value of the alkali-soluble resin is preferably 10 to 170 mgKOH / g, more preferably 20 to 150 mgKOH / g, and further preferably 30 to 140 mgKOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the alkali-soluble resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

[0229] In addition, other examples of the resin include high refractive index resins. A high refractive index resin refers to a resin having a refractive index of 1.60 or more at a wavelength of 550 nm.

[0230] 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, 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.

[0231] 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, more preferably 70% by mass or less.

[0232] (Curable compounds other than component (A) and component (B))

[0233] The composition may contain one or more curable compounds other than component (A) and component (B). By making the composition contain curable compounds other than component (A) and component (B), the viscosity or solvent resistance of the composition can be adjusted, and the mechanical properties and / or optical properties of the resulting cured product and the molded article containing the same can be adjusted.

[0234] Examples of curable compounds other than component (A) and component (B) include epoxy compounds other than component (A) and component (B), oxetane compounds other than component (A), hydroxy compounds, vinyl ether compounds, allyl compounds, thiol compounds, polyphenol compounds, isothiocyanate compounds, acid anhydrides, and the like.

[0235] When the composition contains curable compounds other than component (A) and component (B), based on the total amount of the solid components of the composition, the content of curable compounds other than component (A) and component (B) is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less.

[0236] (Solvent)

[0237] The composition may contain one or more than two solvents. The solvent is preferably a solvent capable of dissolving or dispersing the component (A), and more preferably a solvent capable of also dissolving or dispersing other components other than the component (A). As the solvent, for example, solvents (organic solvents) exemplified in the reaction of the compound represented by the formula (II-1a) and the compound represented by the formula (II-1b), 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, etc. can be mentioned.

[0238] As the ester solvents, 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, etc. can be mentioned.

[0239] As the ether solvents, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methylanisole, etc. can be mentioned.

[0240] As the ether ester solvents, 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. can be mentioned.

[0241] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, etc.

[0242] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, etc.

[0243] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, etc.

[0244] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0245] 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.

[0246] <Cured product and molded article>

[0247] The cured product of one embodiment is the cured product of the composition. The molded article 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, etc., it can be suitably used as a curable material for producing a cured product or a molded article containing the same. The cured product can be obtained by curing the components (A), (B), 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 article 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 article, etc.

[0248] As a method for obtaining a molded article from the composition, there is no particular limitation, and examples include a method of forming a film on a substrate and then performing molding by etching, etc., an injection molding method, a casting polymerization molding method, etc.

[0249] 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, etc., and the obtained molded article is taken out. It is also possible to further irradiate the taken-out molded article with active energy rays to additionally perform curing.

[0250] When forming a film as a molded article 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 article as a cured film (cured layer). The molded article can also be a patterned cured film. The patterned cured film can be obtained by patterning using methods 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 the 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.

[0251] 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 aluminum, silver, silver / copper / palladium alloy thin films, etc. on these substrates. Examples of the coating method of the composition on the substrate include spin coating method, slit coating method, slit and spin coating method, etc.

[0252] The light source used in the exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, a 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.

[0253] After pattern exposure, it is also possible to perform a heat treatment (pre-bake before development) on the exposed coating film before development. For a composition containing a compound having an epoxy group or an oxetanyl group, if pre-bake 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 component (A) (a compound having at least one thiiranyl or thietanyl group), there is a tendency that a patterned cured film can be easily obtained by development even without pre-bake before development. Therefore, by using the composition of the present embodiment, the pre-bake before development process can be omitted in the exposure and development processes, and the productivity of the molded article can be improved.

[0254] As a developer used in development, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, 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 (II-1a) and the compound represented by the formula (II-1b) 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-bake) the patterned cured film obtained by development.

[0255] The cured product or the molded product containing the same is formed from the composition, and thus, it 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 at a wavelength of 550 nm of the cured product or the molded product containing the same 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 at a wavelength of 550 nm of the cured product or the molded product containing the same is, for example, 2.000 or less, and can also be 1.900 or less.

[0256] 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, the Δψ spectrum is measured using an ellipsometer (manufactured by J.A. Woollam Co., Ltd., "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. Thereby, the refractive index at a wavelength of 550 nm of the cured product or the molded product containing the same can be obtained.

[0257] <Use and Application>

[0258] Use as a solidified product or a molded product, for example, glass substitutes and surface coating materials thereof can be mentioned; 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 such coatings; alkyd resin spray paints and coating films formed using such paints; acrylic spray paints and coating films formed using such paints; components for light sources that emit ultraviolet rays such as fluorescent lamps and mercury lamps; materials for blocking electromagnetic waves, etc. 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, sheets or films for agricultural and industrial use; anti-fading agents for printed matter, dyed matter, dyes, pigments, etc.; protective films for polymer supports (for example, for plastic components of mechanical and automotive parts); protective coatings for printed matter; inkjet medium coatings; laminated light-shielding materials; optical light films; interlayers for safety glass / windshields; electrochromic / photochromic uses; 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 decorations for homes such as curtains, carpets, wallpapers, etc.; medical devices 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 encapsulating materials, etc.

[0259] The molded product can be suitably used as an optical supply, 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 can be used for the purpose of improving the light collection efficiency into each photoelectric conversion element. In addition, in the display device, a lens can be used for the purpose of improving the light extraction efficiency from pixels. The lens can be a microlens. Examples of the display device include a liquid crystal display device, an organic EL display device, etc.

[0260] As high refractive index materials, inorganic compounds such as zirconium oxide and titanium oxide have been known in the past. However, in the case of producing a molded product 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. In addition, 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 as an organic compound.

[0261] Examples

[0262] Hereinafter, examples will be given to more specifically illustrate the present invention. However, the present invention is not limited to these examples. It should be noted that hereinafter, unless otherwise specified, "parts" means "parts by mass".

[0263] [Synthesis Example 1]

[0264] [Synthesis of Compound (A-1)]

[0265] ·Synthesis of Compound (A-1a)

[0266]

[0267] 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 it was stirred in an ice bath for 15 minutes. Next, 15 parts of sodium hydroxide, 66 parts of acetone, and 203 parts of pure water were added to another flask, and after completely dissolving them, 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 obtained mixture was purified to obtain 46 parts of a compound represented by the formula (A-1a) (Compound (A-1a)).

[0268] Perform 1 1H-NMR analysis and LC-MS measurement to confirm the formation of Compound (A-1a).

[0269] 1 1H-NMR (deuterated chloroform) δ: 8.37 - 8.39 (1H), 7.85 (1H), 7.39 - 7.70 (4H), 3.08 - 3.29 (5H), 2.94 - 2.98 (1H), 2.57 - 2.81 (3H), 2.39 - 2.41 (1H)

[0270] LC-MS: [M + H] + = 305.5

[0271] ·Synthesis of Compound (A-1)

[0272]

[0273] The inside of a four-necked flask equipped with a Dimroth condenser and a thermometer was made into a nitrogen atmosphere, 3 parts of Compound (A-1a), 30 parts of methanol, 30 parts of toluene, 0.05 part of acetic anhydride, and 3.8 parts of thiourea were added to the above flask, and it was stirred at room temperature for 24 hours. The obtained mixture was purified to obtain 2.5 parts of a compound represented by the formula (A-1) (Compound (A-1)).

[0274] Perform 1 H-NMR analysis and LC-MS determination were carried out to confirm the formation of compound (A-1).

[0275] 1 H-NMR (chloroform-d) 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)

[0276] LC-MS: [M + H] + = 337.5

[0277] [Synthesis Example 2]

[0278] [Synthesis of Compound (D-1)-1]

[0279]

[0280] 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, 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 the compound represented by the formula (D-1) (compound (D-1)).

[0281] Perform 1 H-NMR analysis and LC-MS determination were carried out to confirm the formation of compound (D-1).

[0282] 1 H-NMR (chloroform-d) δ: 10.07 (2H), 8.40 - 8.43 (1H), 7.90 (1H), 7.72 - 7.74 (2H), 7.54 - 7.56 (1H), 7.34 - 7.37 (1H), 3.69 - 3.89 (2H), 1.47 - 1.51 (6H)

[0283] LC-MS: [M - H] + = 335.2

[0284] [Synthesis of Compound (D-1)-2]

[0285]

[0286] Using a method different from the above method, the compound represented by formula (D-1) (compound (D-1)) was synthesized. 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, 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 (D-1) (compound (D-1)).

[0287] [Synthesis Example 3]

[0288] [Synthesis of Compound (D-2)]

[0289]

[0290] The inside of a four-necked flask equipped with a Dimroth condenser and a thermometer was made into a nitrogen atmosphere, 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 (D-2) (compound (D-2)).

[0291] Perform 1 1H-NMR analysis and LC-MS measurement to confirm the formation of compound (D-2).

[0292] 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)

[0293] LC-MS: [M-H] + = 363.2

[0294] [Synthesis Example 4]

[0295] [Synthesis of Compound (D-3)]

[0296]

[0297] The inside of a four-necked flask equipped with a Dimroth condenser and a thermometer was made into a nitrogen atmosphere, 5 parts of 1,6-naphthalenedithiol, 9.8 parts of 3-chloro-2,2-dimethylpropionic acid, 12.5 parts of acetone, 50 parts of pure water, and 5.2 parts of sodium hydroxide were added to the above flask, and the mixture was stirred at 75 °C for 3 hours. The obtained mixture was purified to obtain 10.1 parts of the compound represented by formula (D-3) (compound (D-3)).

[0298] Perform 1 H-NMR analysis and LC-MS determination were carried out to confirm the formation of compound (D-3).

[0299] 1 H-NMR (chloroform-d) 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)

[0300] LC-MS: [M-H] + = 391.2

[0301] [Synthesis Example 5]

[0302] [Synthesis of Compound (D-4)]

[0303]

[0304] The inside of a four-necked flask equipped with a Dimroth condenser and a thermometer was made into a nitrogen atmosphere, 5 parts of 1,6-naphthalenedithiol, 7 parts of 3-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 6.8 parts of a compound represented by the formula (D-4) (compound (D-4)).

[0305] Perform 1 H-NMR analysis and LC-MS determination were carried out to confirm the formation of compound (D-4).

[0306] 1 H-NMR (chloroform-d) 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)

[0307] LC-MS: [M-H] + = 363.2

[0308] [Synthesis Example 6]

[0309] [Synthesis of Compound (D-5)]

[0310]

[0311] Make the atmosphere in a four-necked flask equipped with a Dimroth condenser and a thermometer 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 (D-5) (compound (D-5)).

[0312] Carry out 1 H-NMR analysis and LC-MS measurement to confirm the formation of compound (D-5).

[0313] 1 H-NMR (deuterochloroform) 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)

[0314] LC-MS: [M-H] + = 419.2

[0315] [Synthesis Example 7]

[0316] [Synthesis of Compound (D-6)]

[0317]

[0318] 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, 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 (D-6) (compound (D-6)).

[0319] Carry out 1 H-NMR analysis and LC-MS measurement to confirm the formation of compound (D-6).

[0320] 1 H-NMR (deuterochloroform) 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)

[0321] LC-MS: [M-H] + = 419.2

[0322] [Synthesis Example 8]

[0323] [Synthesis of Compound (D-7)]

[0324]

[0325] The compound represented by formula (D-7) (Compound (D-7)) was synthesized according to the method described in International Publication No. 2023 / 058449.

[0326] [Examples 1 to 15 and Comparative Examples 1 to 4]

[0327] [Preparation of Composition]

[0328] The compounding ingredients shown in Table 1 were charged into a flask in the addition amounts shown in Table 1 (unit: parts by mass), and stirred to prepare the liquid compositions of Examples 1 to 15 and Comparative Examples 1 to 4. The compositions of Examples 1 to 15 and Comparative Examples 1 to 4 were transparent to the naked eye, and it was confirmed that the compounding ingredients were uniformly dissolved.

[0329] Details of the abbreviations of the compounding ingredients shown in Table 1 are as described below.

[0330] Component (A): A compound having at least one thiiranyl or thietanyl group

[0331] · (A-1): The compound (A-1) synthesized in Synthesis Example 1

[0332] Component (B): An alicyclic epoxy compound having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized

[0333] · (B-1): A compound having at least one structure in which an alicyclic unsaturated hydrocarbon is epoxidized (manufactured by Daicel Corporation, "Celloxide 2021P")

[0334] · (B-2): A compound having at least one structure in which an alicyclic unsaturated hydrocarbon is epoxidized (manufactured by Daicel Corporation, "Celloxide 8010")

[0335] · (B-3): A compound having at least one structure in which an alicyclic unsaturated hydrocarbon is epoxidized (manufactured by Daicel Corporation, "Celloxide 2081")

[0336] · (B-4): A compound having at least one structure in which an alicyclic unsaturated hydrocarbon is epoxidized (manufactured by Daicel Corporation, "Epolead GT401")

[0337] ·(B-5): A compound having a structure formed by epoxidizing at least one alicyclic unsaturated hydrocarbon (manufactured by ENEOS Corporation, "EPOCHALIC THI-DE")

[0338] (Component (b)): A curable compound other than component (B)

[0339] ·(b-1): An oxetane compound having no alicyclic ring in the molecule (manufactured by Toagosei Co., Ltd., "ARON OXETANE OXT-121")

[0340] ·(b-2): An epoxy compound having no alicyclic ring in the molecule (manufactured by Nagase Chemtex Corporation, "Denacol EX-201")

[0341] (Component (C)): A photoacid generator

[0342] ·(C-1): An aromatic sulfonium salt (manufactured by San-Apro Ltd., "VC-1FG")

[0343] ·(C-2): An aromatic sulfonium salt (manufactured by San-Apro Ltd., "VC-1S")

[0344] (Component (D)): A compound having a group represented by formula (Z)

[0345] ·(D-1): The compound (D-1) synthesized in Synthesis Example 2

[0346] ·(D-2): The compound (D-2) synthesized in Synthesis Example 3

[0347] ·(D-3): The compound (D-3) synthesized in Synthesis Example 4 · (D-4): The compound (D-4) synthesized in Synthesis Example 5 · (D-5): The compound (D-5) synthesized in Synthesis Example 6 · (D-6): The compound (D-6) synthesized in Synthesis Example 7 · (D-7): The compound (D-7) synthesized in Synthesis Example 8 Solvent

[0348] ·(E-1): PGMEA (propylene glycol monomethyl ether acetate) [Table 1]

[0349]

[0350] <Evaluation Test>

[0351] (1) Film-forming property

[0352] For the compositions of Examples 1 to 15 and Comparative Examples 1 to 4, a coating film was formed by the following method to evaluate the film-forming property. About 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 Inc., "Eagle XG"), 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 alkali-free glass plate with the coating film formed thereon was heated at 60 °C for 2 minutes to remove the solvent.

[0353] 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 the opening defect means 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. The depression defect means the following state: Although the exposed part of the alkali-free glass plate is not observed, the local film thickness becomes thinner centering on environmental foreign matters, etc., and a pit-shaped defect with a diameter of less than 1 mm is generated. The results are shown in Table 2.

[0354] 5: Colorless and transparent, and neither opening defect nor depression defect is observed.

[0355] 4: Two or more and less than five depression defects are observed.

[0356] 3: Two or more and less than five opening defects are observed.

[0357] 2: Two or more and less than five opening defects and two or more and less than five depression defects are respectively observed.

[0358] 1: Five or more opening defects and five or more depression defects are respectively observed.

[0359] (2) Formation of cured film

[0360] About 3 mL of the compositions of Examples 1 to 15 and Comparative Examples 1 to 4 were respectively dropped onto the polished surfaces of silicon wafers (thickness: 0.5 mm, diameter: 4 inches, manufactured by Rokko 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 wafers with the coating films formed thereon were heated at 60 °C for 2 minutes to remove the solvent. For the obtained coating films, on the silicon wafers with the cured films formed thereon, using a high-pressure mercury lamp proximity UV exposure device (manufactured by USHIO INC., "UV-3300SC"), in an air atmosphere, using 1000 mJ / cm 2The irradiation energy was used for proximity exposure through a photomask with a 200-μm gap between the photomask and the coating surface. For the obtained silicon wafer, post-baking was performed by heating 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.

[0361] (3) Solvent resistance (film thickness retention rate)

[0362] 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 the solvent resistance, the silicon wafer with the cured film formed thereon was immersed in acetone at 23°C for 10 minutes, and the 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.

[0363] 5: The film thickness retention rate is 95% or more and 100% or less.

[0364] 4: The film thickness retention rate is 90% or more and less than 95%.

[0365] 3: The film thickness retention rate is 80% or more and less than 90%.

[0366] 2: The film thickness retention rate is 50% or more and less than 80%.

[0367] 1: The film thickness retention rate is less than 50%.

[0368] (4) Measurement of refractive index

[0369] 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., "M-2000"), and 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.

[0370] (5) Alkaline developability

[0371] About 3 mL of the composition of Examples 1 to 15 and Comparative Examples 1 to 4 was dripped onto the polished surface of a silicon wafer (0.5 mm thick, 4 inches in diameter, manufactured by Rokko Electronics Co., Ltd.), and spin-coated at 1000 rpm and 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 was heated at 60°C for 2 minutes to remove the solvent. Next, a high-pressure mercury lamp proximity UV exposure device (manufactured by USHIO INC., "UV-3300SC") was used to expose the silicon wafer in an atmospheric atmosphere using 1000 mJ / cm 2 The irradiation energy was irradiated with a photomask and proximity exposure was performed with a gap of 200 μm between the photomask and the coated surface. Subsequently, the wafer was immersed in a 2.38% by mass aqueous solution of TMAH (tetramethylammonium hydroxide) for 1 minute and then immersed in pure water for 1 minute for development. It should be noted that in Comparative Example 4, the silicon wafer with the coating film formed thereon after exposure was heated at 80°C for 2 minutes as PEB and then developed. Subsequently, the wafer was heated at 120°C for 5 minutes using a hot plate to obtain a silicon wafer with a patterned cured film formed thereon.

[0372] The pattern-formability of the patterned cured film was evaluated based on the following evaluation criteria. The results are shown in Table 2.

[0373] 5: Line width is less than 3μm.

[0374] 4: The line width is 3 μm or more and less than 5 μm.

[0375] 3: The line width is 5 μm or more and less than 10 μm.

[0376] 2: The unexposed portion was completely insoluble in the developer, and no pattern was formed.

[0377] 1: The exposed portion and the unexposed portion were completely dissolved in the developer, and no pattern was formed.

[0378] For patterned cured films with a patternability rating of 3 to 5, the difference in film thickness between the exposed and unexposed areas after development was measured, and the dissolution contrast was evaluated based on the following evaluation criteria. Causes of reduced dissolution contrast include insufficient dissolution in the unexposed areas and dissolution in the exposed areas. The results are shown in Table 2.

[0379] 5: The difference in film thickness between the exposed portion and the unexposed portion after development is 1.3 μm or more and 1.5 μm or less.

[0380] 4: The difference in film thickness between the exposed portion and the unexposed portion after development is 1.0 μm or more and less than 1.3 μm.

[0381] 3: The film thickness difference between the exposed part and the unexposed part after development is 0.5 μm or more and less than 1.0 μm.

[0382] 2: The film thickness difference between the exposed part and the unexposed part after development is 0.1 μm or more and less than 0.5 μm.

[0383] 1: The film thickness difference between the exposed part and the unexposed part after development is less than 0.1 μm.

[0384] [Table 2]

[0385]

[0386] As shown in Table 2, compared with the composition of the comparative example, the composition of the example has a sufficiently high refractive index and excellent solvent resistance. 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 solvent resistance.

Claims

1. A composition comprising: a compound having at least one thiiranyl or thietanyl group; an alicyclic epoxy compound having a structure formed by epoxidation of an alicyclic unsaturated hydrocarbon; a photoacid generator; and a compound having a group represented by formula (Z), wherein in formula (Z), A represents a hydrogen atom or a cation, * represents a bonding position.

2. The composition according to claim 1, wherein, The compound having at least one thiiranyl or thietanyl group includes a compound represented by formula (II), wherein 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 As 1x which may be the same or different; among them, at least one of the two As 1x is a sulfur atom; mx represents 0 or 1, and when there are two mx, they may be the same or different; nx represents any integer from 0 to 6; R 1x represents a monovalent substituent, R 1x When there are multiple ones present, 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.

3. The composition according to claim 1, wherein, The alicyclic epoxy compound having a structure formed by epoxidation of an alicyclic unsaturated hydrocarbon is a compound having at least two structures formed by epoxidation of alicyclic unsaturated hydrocarbons in one molecule.

4. The composition according to claim 1, wherein, The compound having a group represented by formula (Z) includes a compound represented by formula (I), wherein in formula (I), L represents a branched alkylene group having 2 to 20 carbon atoms which may have substituents, and when there are two L, they may be the same or different; A represents the same meaning as described above, and when there are two A, they may be the same or different; n represents any integer from 0 to 6; R represents a monovalent substituent, and when there are multiple Rs, the multiple Rs may be the same or different.

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

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

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

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

Images