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

Abstract

Provided is a composition which contains a compound having at least one thiirane group or thietanyl group, and which is capable of forming a cured product having excellent storage stability and excellent curability and heat resistance. The composition contains a compound (A) having at least one thiirane group or thietanyl group, and at least one compound (B) selected from the group consisting of a compound having a skeleton represented by formula (I) and a salt thereof, and a compound having a skeleton represented by formula (II) and a salt thereof. In formula (I), R1A represents a hydrocarbon group or the like, and in formula (II), R2A represents a hydrocarbon group or the like. Each dotted line represents two single bonds or one double bond. # imgabs0 #

Description

Technical Field

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

[0002] In the field of optical devices, there is an urgent need for high-refractive-index materials. Lenses can be obtained using high-refractive-index materials, and the optical path within an optical device can be controlled using the lenses. In a solid-state imaging device, lenses are used for the purpose of improving the light condensing efficiency of each photoelectric conversion element, and in a display device, lenses are 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] The inventors of the present invention have conducted research on high-refractive-index materials and found that a compound having at least one thiiranyl group or thietanyl group is useful as a high-refractive-index material. However, a composition containing such a compound or a cured product thereof cannot satisfy curability, heat resistance, and storage stability at a high level, and there is room for improvement.

[0007] Therefore, the main object of the present invention is to provide a composition containing a compound having at least one thiiranyl group or thietanyl group, which can form a cured product having excellent storage stability, curability, and heat resistance.

[0008] The present invention provides the composition described in [1] to [5], the molded product described in [6], the cured product described in [7], the display device described in [8], and the solid-state imaging device described in [9].

[0009] [1] A composition containing:

[0010] Compound (A) having at least one of a thiiranyl group or a thietanyl group, and

[0011] Compound (B) selected from at least one of a compound having a skeleton represented by formula (I) and a salt thereof, and a compound having a skeleton represented by formula (II) and a salt thereof.

[0012]

[0013] [In formula (I), R 1A represents a hydrogen atom or a hydrocarbon group which may have a substituent.]

[0014]

[0015] [In formula (II), R 2A represents a hydrocarbon group which may have substituents or -P(=NR 2x1 )(N(R 2x2 )2)2.

[0016] R 2x1 and R 2x2 each independently represent a hydrocarbon group which may have substituents, and a plurality of R 2x2 may be the same or different from each other.

[0017] Each dashed line represents two single bonds or one double bond.]

[0018] [2] The composition according to [1], wherein the compound (B) is at least one selected from organic carboxylates of compounds having a skeleton represented by formula (I) and organic carboxylates of compounds having a skeleton represented by formula (II).

[0019] [3] The composition according to [1] or [2], wherein the compound having a skeleton represented by formula (I) is a compound represented by formula (I-2).

[0020]

[0021] [In formula (I-2), R 1A has the same meaning as described above.

[0022] Ring X 1A and ring X 1B each independently represent an aliphatic heterocycle which may have substituents.]

[0023] [4] The composition according to any one of [1] to [3], further comprising a polymerization inhibitor (C).

[0024] [5] The composition according to any one of [1] to [4], wherein the compound (A) is a compound represented by formula (A-1).

[0025]

[0026] [In formula (A-1), L represents a single bond or a divalent group, and two Ls may be the same or different.

[0027] A 1 represents an oxygen atom or a sulfur atom, and two As 1 may be the same or different. However, at least one of the two As 1 is a sulfur atom.

[0028] m represents 0 or 1, and the two m's can be the same or different.

[0029] n represents any integer from 0 to 6.

[0030] R 1 represents a monovalent substituent. When there are multiple R's, 1 the multiple R's can be the same or different. 1

[0031] R 2 represents a hydrogen atom or a monovalent substituent, and the two R's 2 can be the same or different.

[0032] [6] A molded article obtained by curing the composition according to any one of [1] to [5].

[0033] [7] A cured product which is a cured product of the composition according to any one of [1] to [5].

[0034] [8] A display device comprising the cured product according to [7].

[0035] [9] A solid-state imaging device comprising the cured product according to [7].

[0036] According to the present invention, a composition can be provided which contains a compound having at least one thiiranyl group or thietanyl group and can form a cured product having excellent storage stability and excellent curability and heat resistance. In addition, 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 Description of the Invention

[0037] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0038] In this specification, a numerical range indicated by "~" represents a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively. In the numerical ranges described in segments 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 other numerically described ranges. In addition, in the numerical ranges 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.

[0039] In this specification, (meth)acrylate means acrylate or the corresponding methacrylate. The same applies to other similar expressions such as (meth)acryloyl and (meth)acrylate.

[0040] ​In this specification, unless otherwise specified, among the materials exemplified below, one kind can be used alone or two or more kinds can be used in combination within the scope of meeting the conditions. When there are multiple corresponding substances in each component, unless otherwise specified, the content of each component refers to the total amount of these multiple substances.

[0041] <Composition>

[0042] The composition of one embodiment contains compound (A) and compound (B). Compound (A) has at least one thiiranyl or thietanyl group, and compound (B) is selected from at least one of a compound having a skeleton represented by formula (I) and its salt, and a compound having a skeleton represented by formula (II) and its salt. The composition according to this embodiment can form a cured product with excellent storage stability, curability, and heat resistance. The composition of this embodiment may further contain a polymerization inhibitor (C), etc.

[0043] (A) component: Compound (A)

[0044] The composition of this embodiment contains component (A). Component (A) can be a curable compound. By making the composition contain component (A), component (A) polymerizes, and a cured product with a high refractive index can be formed.

[0045] As long as component (A) is a compound having at least one thiiranyl or thietanyl group, it can be used without particular limitation. Component (A) can be, for example, a compound having at least one group represented by formula (X0), and preferably a compound having at least one group represented by formula (X1).

[0046]

[0047] In formula (X0),

[0048] m represents 0 or 1.

[0049] R 2 represents a hydrogen atom or a monovalent substituent.

[0050] * represents the bonding position.

[0051]

[0052] In formula (X1), L represents a single bond or a divalent group.

[0053] m represents 0 or 1.

[0054] R 2 represents a hydrogen atom or a monovalent substituent.

[0055] * represents the bonding position.

[0056] Examples of the divalent group represented by L include divalent aliphatic chain hydrocarbon groups which may have substituents; divalent alicyclic hydrocarbon groups which may have substituents; divalent aromatic hydrocarbon groups which may have substituents; divalent hydrocarbon groups composed of combinations thereof (e.g., arylalkylidene), 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—.

[0057] Examples of the divalent aliphatic chain hydrocarbon group include saturated or unsaturated aliphatic chain hydrocarbon groups. More specifically, examples include alkanediyl groups such as methylene, vinyl, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl, undecanediy, dodecanediyl, tridecanediyl, tetradecanediyl, pentadecanediyl, hexadecanediyl, heptadecanediyl, octadecanediyl, nonadecanediyl, icosanediyl, 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, further preferably 1 to 4, and particularly preferably 1 or 2.

[0058] Examples of the substituents which the divalent aliphatic chain hydrocarbon group may have include halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0059] Examples of the divalent alicyclic hydrocarbon group include saturated or unsaturated alicyclic hydrocarbon groups. More specifically, monocyclic alicyclic hydrocarbon groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cyclooctanediyl, cyclononanediyl, cyclodecanediyl; polycyclic alicyclic hydrocarbon groups such as bicyclo[1.1.0]butanediyl, tricyclo[2.2.1.0]heptanediyl, bicyclo[3.2.1]octanediyl, bicyclo[2.2.2]octanediyl, adamantanediyl, bicyclo[4.3.2]undecanediyl, tricyclo[5.3.1.1]dodecanediyl, etc. The number of carbon atoms of the divalent alicyclic hydrocarbon group is usually 3 to 20, preferably 3 to 10, more preferably 3 to 6, further preferably 5 or 6.

[0060] Examples of the substituents which the divalent alicyclic hydrocarbon group may have include alkyl groups having 1 to 10 (preferably 1 to 4) carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0061] The divalent aromatic hydrocarbon group can be monocyclic or polycyclic. Examples of the divalent aromatic hydrocarbon group include phenylene, naphthylene, anthracenediyl, fluorenylene, etc. The number of carbon atoms of the divalent aromatic hydrocarbon group is usually 6 to 20, preferably 6 to 10.

[0062] Examples of the substituent that can have a divalent aromatic hydrocarbon group 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; cyano group, etc.

[0063] As for the monovalent substituent represented by R 2 Examples include monovalent hydrocarbon groups such as a monovalent aliphatic chain hydrocarbon group which may have a substituent, a monovalent alicyclic hydrocarbon group which may have a substituent, a monovalent aromatic hydrocarbon group which may have a substituent, and a monovalent group composed of a combination thereof (such as aralkyl); a monovalent heterocyclic group which may have a substituent; a hydroxyl group; an amino group which may be substituted by one or two alkyl groups having 1 to 6 carbon atoms such as amino group, monomethylamino group, monoethylamino group, dimethylamino group, diethylamino group, and methylethylamino group; a halogen atom; a nitro group; a cyano group; a carboxyl group; a sulfo group; a mercapto group; a formyl group; a -SF3 group; a -SF5 group. The methylene (-CH2-) contained in the monovalent substituent can be substituted by -O-, -S-, -NR B -(R B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO- or -SO2-. It should be noted that as the group after the methylene (-CH2-) contained in the monovalent substituent is substituted by -O-, alkoxy groups having 1 to 12 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, etc.; alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, and methoxyethyl can be cited.

[0064] Examples of the monovalent aliphatic chain hydrocarbon group include saturated or unsaturated aliphatic chain hydrocarbon groups. More specifically, examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl. 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.

[0065] Examples of the substituent that can have a monovalent aliphatic chain hydrocarbon group include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0066] As a monovalent alicyclic hydrocarbon group, for example, a saturated or unsaturated alicyclic hydrocarbon group can be cited. More specifically, monocyclic alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclononyl, cyclodecyl, etc. can be cited; polycyclic alicyclic hydrocarbon groups such as bicyclo[1.1.0]butyl, tricyclo[2.2.1.0]heptyl, bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, adamantyl, bicyclo[4.3.2]undecyl, tricyclo[5.3.1.1]dodecyl, etc. can be cited. The number of carbon atoms of the monovalent alicyclic hydrocarbon group is usually 3 to 20, preferably 3 to 10, more preferably 3 to 6, and further preferably 5 or 6.

[0067] As a substituent that may have a monovalent alicyclic hydrocarbon group, for example, alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. can be cited; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc.; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0068] 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.

[0069] As a substituent that may have a monovalent aromatic hydrocarbon group, for example, alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. can be cited; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc.; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0070] As a monovalent heterocyclic group, for example, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, oxolinyl, thiazolyl, piperidinyl, morpholinyl, piperazinyl, indolyl, isoindolyl, quinolinyl, thiophenyl, pyrrolyl, furyl, etc., which are aliphatic heterocyclic groups having 4 to 20 carbon atoms or aromatic heterocyclic groups having 3 to 20 carbon atoms, etc. can be cited.

[0071] As a substituent that may have a monovalent heterocyclic group, for example, alkyl groups having 1 to 10 carbon atoms (preferably 1 to 4 carbon atoms) such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. can be cited; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc.; hydroxyl group; amino group; acetyl group; cyano group, etc.

[0072] m represents 0 or 1. When m is 0, it represents the three-membered ring structure of thiiranyl, and when m is 1, it represents the four-membered ring structure of thietanyl. m is preferably 0.

[0073] From the viewpoint of the high refractive index of the cured product, the component (A) preferably contains a compound having an aromatic ring. Examples of the aromatic ring include aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring; aromatic heterocycles such as furan ring, pyrrole ring, benzofuran ring, thiophene ring, benzothiophene ring, indole ring, pyridine ring, quinoline ring, isoquinoline ring, pyridazine ring, pyrimidine ring, and triazine ring. The aromatic ring is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring.

[0074] From the viewpoint of the high refractive index of the cured product, the component (A) is preferably a compound represented by the formula (A-1) (hereinafter, sometimes referred to as "compound (A-1)").

[0075]

[0076] In the formula (A-1),

[0077] L represents a single bond or a divalent group, and the two Ls may be the same or different.

[0078] A 1 represents an oxygen atom or a sulfur atom, and the two As 1 may be the same or different. However, at least one of the two As 1 is a sulfur atom.

[0079] m represents 0 or 1, and the two ms may be the same or different.

[0080] n represents any integer from 0 to 6.

[0081] R 1 represents a monovalent substituent, and when there are a plurality of Rs 1 , the plurality of Rs 1 may be the same or different.

[0082] R 2 represents a hydrogen atom or a monovalent substituent, and the two Rs 2 may be the same or different.

[0083] In the compound (A-1), the two groups represented by the formula (X) can be bonded at any position of the 1st to 8th positions of the naphthalene ring. The groups represented by the formula (X) on the naphthalene ring can be bonded at any two positions of the 1st to 4th positions (5th to 8th positions), or can be bonded at 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 the formula (X) on the naphthalene ring are preferably bonded at 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).

[0084]

[0085] In the formula (X), L, A1 , m, and R 2 represent the same meaning as described above, and * represents the bonding position.

[0086] When the compound (A-1) has one or more monovalent substituents represented by R 1 , the monovalent substituents represented by R 1 can be bonded at any position from 1 to 8 of the naphthalene ring except for the bonding position of the group represented by formula (X).

[0087] L represents a single bond or a divalent group, and the two Ls can be the same or different. In the compound (A-1), at least one of the two Ls is preferably an alkanediyl group, and more preferably both are alkanediyl groups. In this case, the number of carbon atoms of the alkanediyl group is preferably from 1 to 10, more preferably from 1 to 6, further preferably from 1 to 4, and particularly preferably 1 or 2.

[0088] A 1 represents an oxygen atom or a sulfur atom, and the two As 1 can be the same or different. However, at least one of the two As 1 is a sulfur atom. In the compound (A-1), both of the two As 1 are preferably sulfur atoms. As the number of sulfur atoms as A 1 increases, a cured product having a higher refractive index can be formed, and there is a tendency for the curability to be more excellent.

[0089] m represents 0 or 1, and the two ms can be the same or different. In the compound (A-1), both of the two ms are preferably 0.

[0090] n represents any integer from 0 to 6. n is preferably any integer from 0 to 3, more preferably any integer from 0 to 2, further preferably 0 or 1, and particularly preferably 0.

[0091] R 1 represents a monovalent substituent. When there are multiple Rs 1 , the multiple Rs 1 can be the same or different. Examples of the monovalent substituent represented by R 1 include the same substituents as those represented by R 2 .

[0092] R 2 represents a hydrogen atom or a monovalent substituent, and the two Rs 2 can be the same or different. In the compound (A-1), the two Rs 2Preferably 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.

[0093] As the component (A) (compound (A-1)), for example, compounds represented by the formula (Aa), formula (Ab), formula (Ac), formula (Ad), formula (Ae) and formula (Af) can be cited. L, A in the formula (Aa), formula (Ab), formula (Ac), formula (Ad), formula (Ae) and formula (Af) 1 、m, n, R 1 and R 2 represent the same meaning as described above.

[0094]

[0095] In the formula (Aa), formula (Ab), formula (Ac), formula (Ad), formula (Ae) and formula (Af), at least one of the two Ls is preferably an alkanediyl group, and more preferably both are alkanediyl groups. In this case, the number of carbon atoms of the alkanediyl group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 or 2.

[0096] In the formula (Aa), formula (Ab), formula (Ac), formula (Ad), formula (Ae) and formula (Af), the two m are each independently 0 or 1, and preferably 0. In the formula (Aa), formula (Ab), formula (Ac), formula (Ad), formula (Ae) and formula (Af), the two m are preferably both 0.

[0097] In the formula (Aa), formula (Ab), formula (Ac), formula (Ad), formula (Ae) and formula (Af), n is each independently any integer from 0 to 6, preferably any integer from 0 to 3, more preferably any integer from 0 to 2, still more preferably 0 or 1, and particularly preferably 0.

[0098] In the formula (Aa), formula (Ab), formula (Ac), formula (Ad), formula (Ae) and formula (Af), the two A 1 are each independently an oxygen atom or a sulfur atom. However, at least one of the two A 1 is a sulfur atom. A 1 Preferably both are sulfur atoms.

[0099] In the formula (Aa), formula (Ab), formula (Ac), formula (Ad), formula (Ae) and formula (Af), the two R 2Each is independently preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group, more preferably a hydrogen atom or a monovalent aliphatic chain hydrocarbon group having 1 to 6 carbon atoms, still more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, a methyl group or an ethyl group. Two Rs 2 are preferably the same.

[0100] Specific examples of compound (A-1) are shown below, but are not limited thereto.

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] 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.

[0109] As compound (A-1) of component (A), it can be obtained by synthesizing a compound represented by formula (A-1a) (hereinafter, sometimes also referred to as "compound (A-1a)") and reacting the compound (A-1a) with a sulfurizing agent.

[0110]

[0111] In formula (A-1a), L, m, n, R 1 and R 2 have the same meanings as those represented by the above (formula (A-1)).

[0112] Compound (A-1a) can be obtained, for example, by a method including a step of reacting a compound represented by formula (A-2) (hereinafter, sometimes referred to as "compound (A-2)") with a compound represented by formula (A-3) (hereinafter, sometimes referred to as "compound (A-3)").

[0113]

[0114] In formula (A-2), n and R 1Represents the same meaning as described above.

[0115]

[0116] In formula (A-3), L, m and R 2 Represents the same meaning as described above, and X represents a leaving group.

[0117] The reaction of compound (A-2) with compound (A-3) can be carried out, for example, in the presence of a base. As the base, 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, etc. can be mentioned; metal alkoxides such as sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, sodium isopropoxide, potassium isopropoxide, sodium tert-butoxide, potassium tert-butoxide, etc.; 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, etc. The amount of the base used can be, for example, 0.0001 to 10 moles, preferably 0.001 to 5 moles, more preferably 0.01 to 4 moles, and further preferably 0.1 to 3 moles relative to 1 mole of compound (A-2).

[0118] In addition, two or more bases can be used in combination. In the case of combination, a combination of carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, etc., or bicarbonates such as sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, etc. with metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, etc., 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, etc. is preferred, and a combination of bicarbonate and metal hydroxide is more preferred. In the case of combination, the two can be added simultaneously or stepwise.

[0119] In compound (A-3), as the leaving group represented by X, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc. can be mentioned; alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, trifluoromethylsulfonyl group, perfluoroethylsulfonyl group, perfluoropropylsulfonyl group, perfluorobutylsulfonyl group, etc.; aromatic sulfonyl groups such as benzenesulfonyl group, p-toluenesulfonyl group, p-fluorobenzenesulfonyl group, pentafluorobenzenesulfonyl group, etc. As a specific example of compound (A-3), epihalohydrin compounds (L is methylene, m is 0, R 2a compound in which A is a hydrogen atom and X is a halogen atom). The amount of the compound (A-3) used can be, for example, 0.01 to 20 moles, preferably 0.5 to 15 moles, per 1 mole of the compound (A-2). In this step, the reaction can be carried out using two or more compounds (A-3).

[0120] The reaction between the compound (A-2) and the compound (A-3) is preferably carried out in a solvent. Examples of the solvent include, 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, and amides. Specific examples of the organic solvents are shown below.

[0121] 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.;

[0122] Aromatic hydrocarbons: benzene, toluene, xylene, mesitylene, naphthalene, anisole, nitrobenzene, aniline, tetralin, durene, etc.;

[0123] Halogenated aromatic hydrocarbons: chlorobenzene, dichlorobenzene, chloronaphthalene, etc.;

[0124] Aliphatic hydrocarbons: pentane, hexane, heptane, etc.;

[0125] Halogenated aliphatic hydrocarbons: dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, tetrachloroethylene, etc.;

[0126] Ethers: diethyl ether, diisopropyl ether, methyl tert-butyl ether, cyclopentyl methyl ether, diphenyl ether, dimethoxyethane, dioxane, etc.; Alcohols: methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, hexafluoroisopropanol, etc.;

[0127] Glycol dimethyl ethers: methyl diglycol dimethyl ether, ethyl diglycol dimethyl ether, triglycol dimethyl ether, diethylene glycol butyl methyl ether, etc.;

[0128] Esters: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, etc.;

[0129] Aliphatic nitriles: acetonitrile, etc.;

[0130] Sulfoxides: dimethyl sulfoxide, sulfolane, etc.;

[0131] Amides: N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

[0132]

[0133] ​The reaction temperature of compound (A-2) and compound (A-3) can be, for example, -80 to 200 °C, preferably -40 to 150 °C, more preferably -20 to 120 °C, and still more preferably -5 to 100 °C.

[0134] Proceeding in this way can obtain compound (A-1a). When using compound (A-1a) obtained in the synthesis of compound (A-1), compound (A-1a) can be used after separation or can be used directly without separation.

[0135] Compound (A-1) can be obtained, for example, by a method including a step of reacting compound (A-1a) with a sulfurizing agent.

[0136] The reaction of compound (A-1a) with a sulfurizing agent is a reaction in which the sulfurizing agent substitutes the oxygen atom of the epoxy ring or oxetanyl ring in compound (A-1a) with a sulfur atom to form a thiirane ring (episulfide ring) or a thietane ring. Examples of the sulfurizing agent include thiourea, methylthiourea, dimethylthiourea, trimethylthiourea, tetramethylthiourea, tetraethylthiourea, ethylenethiourea, phenylthiourea, diphenylthiourea, tolylthiourea, xylylthiourea, sodium thiocyanate, potassium thiocyanate, etc. The amount of the sulfurizing agent used can be arbitrarily adjusted according to the oxygen atom to be substituted. The amount of the sulfurizing agent used is, for example, 0.01 to 20 moles, preferably 0.5 to 10 moles, relative to 1 mole of compound (A-1a). In addition, by adjusting the amount of the sulfurizing agent used, the reaction temperature, the reaction time, etc., two oxygen atoms in compound (A-1a) can be substituted with sulfur atoms, or one oxygen atom in compound (A-1a) can be substituted with a sulfur atom.

[0137] The reaction of compound (A-1a) 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 compound (A-2) and compound (A-3). The reaction of compound (A-1a) with a sulfurizing agent can be, for example, -80 to 200 °C, preferably -40 to 100 °C, more preferably -20 to 80 °C, and still more preferably -5 to 60 °C.

[0138] In order to inhibit the polymerization of the generated compound (A-1), a polymerization inhibitor can also be added to the reaction system. Examples of the polymerization inhibitor include acids, acid anhydrides, etc. More specifically, examples include:

[0139] Inorganic acidic compounds such as nitric acid, hydrogen chloride (hydrochloric acid), perchloric acid, hypochlorous acid, chlorine dioxide, hydrofluoric acid, sulfuric acid, fuming sulfuric acid, thionyl chloride, boric acid, arsenic acid, arsenous acid, pyroarsenic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphorus oxychloride, phosphorus oxybromide, phosphorus sulfide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, hydrocyanic acid, chromic acid, nitric anhydride, sulfuric anhydride, boron oxide, arsenic pentoxide, phosphorus pentoxide, chromium trioxide, 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, etc.;

[0140] Organic carboxylic acids such as formic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, propionic acid, butyric acid, succinic acid, valeric acid, caproic acid, caprylic acid, naphthenic acid, methyl mercaptopropionate, malonic acid, glutaric acid, adipic acid, cyclohexanecarboxylic acid, thiodipropionic acid, dithiodipropionic acid acetate, maleic acid, benzoic acid, phenylacetic acid, o-methylbenzoic acid, m-methylbenzoic acid, p-methylbenzoic 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, etc.;

[0141] Phosphoric acids such as monomethyl phosphate, dimethyl phosphate and trimethyl phosphate, monoethyl phosphate, diethyl phosphate and triethyl phosphate, monoisobutyl phosphate, diisobutyl phosphate and triisobutyl phosphate, monobutyl phosphate, dibutyl phosphate and tributyl phosphate, monolauryl phosphate, dilauryl phosphate and trilauryl phosphate, etc., and phosphorous acids formed by converting the phosphate ester part of these phosphoric acids into phosphite esters;

[0142] Organic phosphorus compounds such as dialkyl dithiophosphoric acids represented by dimethyldithiophosphoric acid, etc.;

[0143] 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, hydroxybenzaldehyde, 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, etc.;

[0144] 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-phenolsulfonic acid, m-benzoic acid, p-aminobenzenesulfonic acid, 4B-acid, disulfonic acid of diamino stilbene, biphenylsulfonic acid, α-naphthalenesulfonic acid, β-naphthalenesulfonic acid, peri-acid, Laurent’s acid, phenyl J-acid and other sulfonic acids, etc.

[0145] 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 relative to 1 mole of the compound (A-1). Among these, the polymerization inhibitor is preferably acetic acid, acetic anhydride, maleic acid, maleic anhydride, phosphoric acid, alkali metal hydrogen phosphate or alkali metal dihydrogen phosphate.

[0146] By washing the reaction product solution with an acidic aqueous solution, the time-dependent stability of the obtained compound (A-1) can be improved. Specific examples of the acid used in the acidic aqueous solution include the acids exemplified as polymerization inhibitors above. This acid can be used alone or in combination of two or more. The acidic aqueous solution generally tends to show 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.

[0147] Furthermore, in order to improve the stability of the compound (A-1), a hydrogen sulfide adsorbent can also be used. Examples of the hydrogen sulfide adsorbent include iron(III) hydroxide, zinc oxide, KNK-301 (a zinc oxide-based adsorbent, manufactured by Kureha Corporation), NIONON202A (an iron oxide-based adsorbent, manufactured by Ibuki Shoji Co., Ltd.), LIMONIC (an iron hydroxide-based, manufactured by Nippon Limonite Co., Ltd.), etc. The hydrogen sulfide adsorbent can be added during the reaction or can also be added and used during the purification after the reaction.

[0148] From the viewpoint of easily obtaining the effects of the present invention sufficiently, based on the total amount of the solid components of the composition, the content of the component (A) can be, for example, 30 to 99% by mass. Based on the total amount of the solid components of the composition, the content of the component (A) is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, preferably 97% by mass or less, more preferably 95% by mass or less, and further preferably 92% by mass or less.

[0149] The total amount of the solid components of the composition refers to the sum of the components contained in the composition excluding the solvent. The content of each component in the solid components of the composition can be determined by known analytical means such as liquid chromatography and gas chromatography. The content of each component in the solid components of the composition can be calculated based on the formulation during the preparation of the composition.

[0150] Component (B): Compound (B)

[0151] The composition of the present embodiment contains component (B). Component (B) is at least one selected from a compound having a skeleton represented by formula (I) (hereinafter sometimes referred to as "compound (I)") and its salt, and a compound having a skeleton represented by formula (II) (hereinafter sometimes referred to as "compound (II)") and its salt. Component (B) can be a component that functions as a base catalyst (anionic polymerization catalyst). That is, component (B) can be a component that releases a base that initiates anionic polymerization by at least one of active energy ray irradiation and heat. By making the composition contain component (A) and component (B), a cured product having excellent storage stability, curability, and heat resistance can be formed. From the viewpoints of curability and heat resistance, component (B) is preferably compound (I) and its salt.

[0152] Compound (I) can also be referred to as, for example, "a compound having a guanidine skeleton (guanidine compound)". Compound (II) can also be referred to as, for example, "a compound having a phosphazene skeleton (phosphazene compound)". By forming salts of these compounds, the storage stability can be improved. Component (B) is preferably a salt of these compounds. From the viewpoints of curability and heat resistance, component (B) is more preferably a salt of compound (I), and further preferably an organic carboxylate salt of compound (I).

[0153]

[0154] In formula (I), R 1A represents a hydrogen atom or a hydrocarbon group that may have a substituent.

[0155] Examples of the hydrocarbon group that may have a substituent include a monovalent aliphatic chain hydrocarbon group that may have a substituent, a monovalent alicyclic hydrocarbon group that may have a substituent, a monovalent aromatic hydrocarbon group that may have a substituent, and a monovalent group composed of a combination thereof (such as an aralkyl). The methylene (-CH2-) contained in the monovalent substituent can be substituted by -O-, -S-, -NR B -(R B represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, or -SO2-. Specific examples of these hydrocarbon groups include the same groups as those exemplified in the monovalent substituents represented by the above R 2 .

[0156] From the viewpoints of curability and heat resistance, R 1A is preferably a hydrocarbon group which may have a substituent.

[0157] Compound (I) is preferably a compound represented by formula (I-1) (hereinafter, sometimes referred to as "compound (I-1)"), and more preferably a compound represented by formula (I-2) (hereinafter, sometimes referred to as "compound (I-2)").

[0158]

[0159] In formula (I-1),

[0160] R 1A has the same meaning as described above.

[0161] R 1B , R 1C , R 1D and R 1E each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent, or a heterocyclic group which may have a substituent.

[0162] R 1A and R 1B , R 1B and R 1C , R 1C and R 1D , R 1D and R 1E , and R 1E and R 1A may be independently bonded to each other to form, together with the adjacent nitrogen atom, an aliphatic heterocycle which may have a substituent.

[0163] R 1B , R 1C , R 1D and R 1E The hydrocarbon group which may have a substituent in 1A may be the same as the hydrocarbon group which may have a substituent in R 1B , R 1C , R 1D and R 1E The heterocyclic group which may have a substituent in 2 may be the same as the heterocyclic group which may have a substituent in the monovalent substituent represented by the above R

[0164] The number of carbon atoms in the aliphatic heterocycle is preferably 3 to 6, more preferably 3 to 4. Examples of the substituent that may have an aliphatic heterocycle 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; cyano group, etc.

[0165]

[0166] In formula (I-2),

[0167] R 1A has the same meaning as described above.

[0168] Ring X 1A and ring X 1B each independently represent an aliphatic heterocycle which may have a substituent.

[0169] The preferred form of the aliphatic heterocycle which may have a substituent in compound (I-2) may be the same as the preferred form of the aliphatic heterocycle which may have a substituent in compound (I-1).

[0170] Hereinafter, specific examples of compound (I) are illustrated, but are not limited thereto.

[0171]

[0172] From the viewpoint of compatibility, the molecular weight of compound (I) is preferably 1000 or less, more preferably 700 or less, and still more preferably 500 or less. From the viewpoint of volatility, compound (I) is preferably 50 or more, more preferably 70 or more, and still more preferably 100 or more.

[0173] The salt of compound (I) is an ionic compound composed of compound (I) and an acid, and is composed of a cation and an anion. Examples of the anion of compound (I) (the anion constituting the acid) include inorganic anions, organic anions, etc. Examples of the anion include hydroxide ion; halide ions such as chloride ion, bromide ion, and iodide ion; carbonate ion; bicarbonate ion; nitrate ion; sulfate ion; sulfite ion; chromate ion; chromate ion; dichromate ion; phosphate ion; cyanide ion; permanganate ion; complex ions such as hexacyanoferrate(III) ion; organic carboxylic acid ions such as formate ion, acetate ion, propionate ion, butyrate ion, and valerate ion, etc.

[0174] From the viewpoints of curability, heat resistance, and storage stability, the anion of compound (I) is preferably an organic carboxylic acid ion. The number of carbon atoms constituting the organic carboxylic acid ion is preferably 1 to 20, more preferably 1 to 10.

[0175] From the viewpoints of the control of reactivity and storage stability, the compound (I) and its salts are preferably salts of the compound (I), and more preferably organic carboxylates of the compound (I).

[0176] Hereinafter, specific examples of the salts of the compound (I) are exemplified, but are not limited thereto.

[0177]

[0178]

[0179] The compound (I) and its salts can be commercially available products, for example.

[0180]

[0181] In formula (II),

[0182] R 2A represents a hydrocarbon group which may have a substituent or -P(=NR 2x1 )(N(R 2x2 )2)2.

[0183] R 2x1 and R 2x2 each independently represent a hydrocarbon group which may have a substituent, and a plurality of R 2x2 may be the same or different from each other.

[0184] Two R 2x2 may be bonded to each other to form an aliphatic heterocycle which may have a substituent together with the adjacent nitrogen atom.

[0185] Each dashed line represents two single bonds or one double bond.

[0186] R 2A 、R 2x1 and R 2x2 The hydrocarbon group which may have a substituent in may be the same as the hydrocarbon group which may have a substituent in R 1A .

[0187] The compound (II) is preferably a compound represented by formula (II-1) (hereinafter, sometimes referred to as "compound (II-1)"), and more preferably a compound represented by formula (II-2) (hereinafter, sometimes referred to as "compound (II-2)").

[0188]

[0189] In formula (II-1),

[0190] R 2A has the same meaning as described above.

[0191] Each dashed line represents two single bonds or one double bond.

[0192] The group represented by -N…L 2A represents -N(R 2A1 )2, -[N = P(N(R 2A2 )2)2] n2A -N = P(N(R 2A3 )2)3 or -N = C(N(R 2A4 )2)2.

[0193] n2A represents any integer from 0 to 3.

[0194] R 2A1 、R 2A2 、R 2A3 and R 2A4 each independently represent a hydrocarbon group which may have substituents, and multiple R 2A1 、R 2A2 、R 2A3 and R 2A4 can be the same or different from each other.

[0195] Two R 2A1 、two R 2A2 、two R 2A3 、and two R 2A4 can independently bond to each other to form, together with the adjacent nitrogen atom or together with the adjacent nitrogen atom and the phosphorus atom adjacent to this nitrogen atom, an aliphatic heterocycle which may have substituents.

[0196] The group represented by -N…L 2B represents -N(R 2B1 )2, -[N = P(N(R 2B2 )2)2] n2B -N = P(N(R 2B3 )2)3 or -N = C(N(R 2B4 )2)2.

[0197] n2B represents any integer from 0 to 3.

[0198] R 2B1 、R 2B2 、R 2B3 and R 2B4 each independently represent a hydrocarbon group which may have substituents, and multiple R 2B1 、R 2B2 、R 2B3 and R 2B4 can be the same or different from each other.

[0199] Two R 2B1 、two R 2B2 、two R2B3 , and two Rs 2B4 can each independently bond to each other to form, together with an adjacent nitrogen atom or together with an adjacent nitrogen atom and a phosphorus atom adjacent to the nitrogen atom, an aliphatic heterocycle which may have substituents.

[0200] The group represented by -N…L 2C represents -N(R 2C1 )2, -[N = P(N(R 2C2 )2)2] n2C -N = P(N(R 2C3 )2)3 or -N = C(N(R 2C4 )2)2.

[0201] n2C represents any integer from 0 to 3.

[0202] R 2C1 , R 2C2 , R 2C3 and R 2C4 each independently represent a hydrocarbon group which may have substituents, and multiple Rs 2C1 , R 2C2 , R 2C3 and R 2C4 may be the same or different from each other.

[0203] Two Rs 2C1 , two Rs 2C2 , two Rs 2C3 , and two Rs 2C4 can each independently bond to each other to form, together with an adjacent nitrogen atom or together with an adjacent nitrogen atom and a phosphorus atom adjacent to the nitrogen atom, an aliphatic heterocycle which may have substituents.

[0204] When the group represented by -N…L 2A is -N(R 2A1 )2, and when the group represented by -N…L 2B is -N(R 2B1 )2, R 2A1 and R 2B1 can bond to each other, and R 2A1 and R 2B1 together with the respectively bonded nitrogen atom and the phosphorus atom adjacent to the nitrogen atom form an aliphatic heterocycle which may have substituents.

[0205] When the group represented by -N…L 2B is -N(R 2B1 )2, and when the group represented by -N…L 2C is -N(R 2C1 )2, R 2B1 and R 2C1 can bond to each other, and R2B1 and R 2C1 together with the nitrogen atom and the phosphorus atom adjacent to the nitrogen atom to which they are respectively bonded form an aliphatic heterocycle which may have substituents.

[0206] R 2A1 、R 2A2 、R 2A3 、R 2A4 、R 2B1 、R 2B2 、R 2B3 、R 2B4 、R 2C1 、R 2C2 、R 2C3 and R 2C4 The hydrocarbyl groups which may have substituents in can be the same as the hydrocarbyl groups which may have substituents in R 1A .

[0207] The preferred mode of the aliphatic heterocycle which may have substituents in compound (II-1) can be the same as the preferred mode of the aliphatic heterocycle which may have substituents in compound (I-1).

[0208]

[0209] In formula (II-2),

[0210] R 2A has the same meaning as above.

[0211] R 2B 、R 2C 、R 2D 、R 2E 、R 2F and R 2G each independently represent a hydrocarbyl group which may have substituents.

[0212] R 2B and R 2C 、R 2C and R 2D 、R 2D and R 2E 、R 2E and R 2F 、and R 2F and R 2G can each independently bond to each other to form an aliphatic heterocycle which may have substituents together with the adjacent nitrogen atom or together with the adjacent nitrogen atom and the phosphorus atom adjacent to the nitrogen atom.

[0213] R 2B 、R 2C 、R 2D 、R 2E 、R 2F and R 2GThe hydrocarbyl group which may have substituents in it may be the same as R 1A The hydrocarbyl group which may have substituents in it may be the same as that in 1A .

[0214] The preferred form of the aliphatic heterocycle which may have substituents in compound (II-2) may be the same as the preferred form of the aliphatic heterocycle which may have substituents in compound (I-1).

[0215] Hereinafter, specific examples of compound (II) are illustrated, but are not limited thereto.

[0216]

[0217] From the viewpoint of compatibility, the molecular weight of compound (II) is preferably 2000 or less, more preferably 1500 or less, and still more preferably 1200 or less. From the viewpoint of volatility, compound (II) is preferably 50 or more, more preferably 100 or more, and still more preferably 150 or more.

[0218] The salt of compound (II) is an ionic compound composed of compound (II) and an acid, and is composed of a cation and an anion. As the anion of compound (II) (the anion constituting the acid), the same anions as those of compound (I) can be exemplified. From the viewpoints of curability, heat resistance and storage stability, the anion of compound (II) is preferably an organic carboxylate ion. The number of carbon atoms constituting the organic carboxylate ion is preferably 1 to 20, more preferably 1 to 10.

[0219] From the viewpoints of controlling reactivity and storage stability, compound (II) and its salt are preferably the salt of compound (II), and more preferably the organic carboxylate salt of compound (II).

[0220] Hereinafter, specific examples of the salt of compound (II) are illustrated, but are not limited thereto.

[0221]

[0222] Compound (II) and its salt can be commercially available products, for example.

[0223] From the viewpoint of improving curability and / or heat resistance, the content of component (B) is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, relative to 100 parts by mass of the total amount of component (A). From the viewpoint of making the physical properties such as the mechanical properties of the cured product good, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less.

[0224] (C) Component: Polymerization inhibitor (C)

[0225] The composition may also contain one or more than two components (C). Whether to contain a polymerization inhibitor in the composition is preferably determined in consideration of the type of component (A). Component (C) is preferably dissolved or dispersed in a solvent. Component (C) contained in the composition may be added during the preparation of the composition or after the production of component (A). By making the composition contain component (C), the unintended polymerization of component (A) is inhibited, and thus the storage stability of the composition can be improved.

[0226] Component (C) may be exemplified by the same substance as the polymerization inhibitor added to the reaction system to inhibit the polymerization of the generated compound (A-1). Component (C) is preferably an organic carboxylic acid, more preferably an organic carboxylic acid having 10 or less carbon atoms, and still more preferably formic acid or acetic acid.

[0227] When the composition contains component (C), from the viewpoint of improving the storage stability of the composition, the content of component (C) is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, still more preferably 0.5 part by mass or more, particularly preferably 1 part by mass or more, preferably 100 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 25 parts by mass or less, and particularly preferably 10 parts by mass or less, based on 100 parts by mass of the total amount of component (A).

[0228] As other components contained in the composition, for example, resins, curable compounds other than component (A), solvents, additives, etc. can be cited. As additives, for example, inorganic particles, fillers, polymerization initiators, thickeners, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, ultraviolet absorbers, antioxidants, dispersants, etc. can be cited.

[0229] (Resin)

[0230] The composition may contain one or more than two resins. By making the composition contain a resin, developability can be imparted to the cured product of the composition, or the mechanical properties and / or optical properties of the cured product and the molded product containing the same can be adjusted. As the resin, for example, thermoplastic resins and curable resins can be cited. The curable resin may be a photocurable resin cured by irradiation with active energy rays or a thermosetting resin cured by heat.

[0231] As thermoplastic resins, for example, 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, vinylidene 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; polyoxymethylene resin; polyamide resin; polycarbonate resin; polyurethane resin; polyphenylene sulfide resin, etc. One or more of these resins can be used as polymer blends or polymer alloys.

[0232] As curable resins, resins having a photopolymerizable group or a thermopolymerizable group can be mentioned. More specifically, for example, (meth)acrylic resins, epoxy resins, melamine resins, unsaturated polyester resins, phenolic resins, urea resins, alkyd resins, polyimide resins, etc. can be mentioned.

[0233] As other examples of resins, alkali-soluble resins can be mentioned. By making the composition contain an alkali-soluble resin, developability can be imparted to the cured product of the composition. An alkali-soluble resin is a resin that is soluble in an aqueous alkali solution. Specifically, for example, resins having a carboxyl group and / or a phenolic hydroxyl group can be mentioned.

[0234] From the viewpoint of improving the developability and solvent resistance of the cured product of the composition, the acid value of the alkali-soluble resin is preferably 10 to 170 mgKOH / g, more preferably 20 to 150 mgKOH / g, and further preferably 30 to 140 mgKOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the alkali-soluble resin, and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

[0235] In addition, as other examples of resins, high refractive index resins can be mentioned. A high refractive index resin means that the refractive index at a wavelength of 550 nm is 1.60 or more.

[0236] The weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC) of the resin can be, for example, 500 to 2,000,000, preferably 1,000 to 1,000,000, and more preferably 1,500 to 750,000. The Mw of the resin can be adjusted by appropriately combining reaction conditions such as the selection of raw materials used, charging methods, reaction temperature, and time.

[0237] When the composition contains a resin, the content of the resin is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 80% by mass or less, and more preferably 70% by mass or less based on the total amount of the solid components of the composition.

[0238] (Curable compound other than component (A))

[0239] The composition may further contain one or more curable compounds other than component (A). By including a curable compound other than component (A) in the composition, the viscosity or curability of the composition can be adjusted, and the mechanical properties and / or optical properties of the resulting cured product and the molded product containing the cured product can be adjusted.

[0240] Examples of the curable compound other than component (A) include epoxy compounds other than component (A), oxetane compounds other than component (A), hydroxyl compounds, vinyl ether compounds, allyl compounds, thiol compounds, polyphenol compounds, isothiocyanate compounds, (meth)acrylate compounds, acid anhydrides, etc. Among these, the curable compound other than component (A) is preferably a (meth)acrylate compound, that is, a compound having at least one (meth)acryloyl group.

[0241] From the viewpoint of curability, the compound having at least one (meth)acryloyl group is preferably a compound having at least one (meth)acryloyl group and not having an acidic functional group. Here, the acidic functional group refers to a group capable of releasing a proton (H + ) such as a carboxyl group (-COOH), a sulfonic acid group (-SO3H), a phosphoric acid group (-PO4H2), a boric acid group (-BO2H2), etc. However, a group that does not have a proton capable of releasing a carboxylate group such as -COONa, a sulfonate group such as -SO3Na, a phosphate group such as -PO4Na2, a borate group such as -BO2Na2, etc. (the proton capable of being released is substituted by an alkali metal ion, etc.) is not included in the acidic functional group. In addition, for the compound having at least one (meth)acryloyl group, from the aspect of excellent film-forming properties and the ability to increase the viscosity of the composition (thicken the composition), and a thick cured film (for example, 1.0 μm or more) can be obtained by using the composition, a compound having at least one (meth)acryloyl group and having a urethane bond in the molecule is preferred.

[0242] When the composition contains a curable compound other than component (A), the content of the curable compound other than component (A) is preferably 1% by mass or more, more preferably 2% by mass or more, preferably 30% by mass or less, and more preferably 20% by mass or less based on the total amount of the solid components of the composition.

[0243] (Solvent)

[0244] The composition may contain one or more than two solvents. The solvent is preferably a solvent capable of dissolving or dispersing component (A), more preferably a solvent capable of further dissolving or dispersing components other than component (A). Examples of the solvent include the solvents (organic solvents) exemplified in the reaction of compound (A-2) and compound (A-3), 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.

[0245] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexyl acetate, γ-butyrolactone, etc.

[0246] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methylanisole, etc.

[0247] Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc.

[0248] As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, etc. can be cited.

[0249] As the alcohol solvent, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol, etc. can be cited.

[0250] As the aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene, etc. can be cited.

[0251] As the amide solvent, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be cited.

[0252] When the composition contains a solvent, the content of the solvent is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, preferably 1000 parts by mass or less, and more preferably 500 parts by mass or less with respect to 100 parts by mass of the total amount of the solid components of the composition. 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.

[0253] <Curable product and molded product>

[0254] The curable product of one embodiment is the curable product of the composition. The molded product of one embodiment is a molded product obtained by curing the composition and contains the curable product of the composition. Since the composition has excellent film-forming properties, curability, etc., it can be suitably used as a curable material for producing a curable product or a molded product containing the curable product. The curable product can be obtained by curing the component (A) etc. in the composition by using at least one of irradiation with active energy rays and heat. The shape of the molded product containing the curable product is not particularly limited and may include a film (membrane) shape, plate shape, lens shape, powder shape, granular shape, non-spherical particle shape, crushed particle shape, porous shape, massive continuum, fibrous shape, tubular shape, hollow filament shape, etc., and can be any shape corresponding to the use of the molded product, etc.

[0255] As a method for obtaining a molded product from the composition, there is no particular limitation, and methods such as forming a film on a substrate and then molding by etching, injection molding method, casting polymerization molding method, etc. can be cited.

[0256] In the casting polymerization molding method, for example, the composition is injected into a molding die, degassing etc. is carried out as needed, then it is cured by heating in an oven, etc., and the obtained molded product is taken out. Further irradiating the taken-out molded product with active energy rays can also perform post-curing.

[0257] When forming a film as a molded article on a substrate, the composition is coated on the substrate and dried as needed to form a coated film (coating layer), and the coated film (coating layer) is cured, whereby a molded article as a cured film (cured layer) can be obtained. The molded article can also be a cured film (cured layer) with a patterned engraving. The cured film with a patterned engraving can be obtained by engraving a pattern by methods such as photolithography, inkjet method, printing method, etc. The pattern engraving method can be, for example, photolithography. Photolithography is a method of coating a composition on a substrate, drying as needed to form a coated film (coating layer), exposing the coated film (coating layer) through a photomask, and developing the exposed coated film (coating layer).

[0258] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass with a silica coating on the surface, and non-alkali glass; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; and substrates with aluminum, silver, silver / copper / palladium alloy thin films, etc. formed on these substrates. Examples of the method for coating the composition on the substrate include spin coating method, slit coating method, slit and spin coating method, etc.

[0259] The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, according to the absorption wavelength of the photoinitiator, light near 436 nm, near 408 nm, or near 365 nm can be selectively extracted from the light with wavelengths in these ranges using a band-pass filter. Specific examples of the light source include mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc. After pattern exposure, the exposed coated film (coating layer) can be heated (pre-baking before development).

[0260] Examples of the developer used for development include aqueous solutions, solvents, etc. containing basic compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. As the solvent, for example, the solvents (organic solvents) exemplified in the reaction of compound (A-2) and compound (A-3) or the above solvents can be used. The developer can also contain a surfactant. Examples of the development method include spin immersion method, dipping method, spraying method, etc. The patterned cured film (cured layer) obtained by development can also be further heated (post-baking).

[0261] The cured product or the molded article containing the cured product is formed from the composition, and thus can exhibit a high refractive index. In addition, their refractive indices 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 article containing the cured product can be 1.65 or more, 1.68 or more, 1.70 or more, 1.72 or more, 1.73 or more, 1.74 or more, 1.75 or more, or 1.76 or more. The refractive index at a wavelength of 550 nm of the cured product or the molded article containing the cured product is, for example, 2.00 or less, and can also be 1.90 or less.

[0262] The refractive index at a wavelength of 550 nm of the cured product or the molded article containing the cured product 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, a visible ultraviolet spectrophotometer (for example, "V-650" manufactured by JASCO Corporation) equipped with an integrating sphere unit (for example, "ISV-922" manufactured by JASCO Corporation) is used to measure the transmission spectrum and the reflection spectrum at wavelengths from 300 nm to 800 nm of the substrate having the cured film formed thereon. Next, the increase and decrease caused by the interference of the reflection spectrum are subtracted from the transmission spectrum and the reflection spectrum to smooth them. In the obtained true reflection spectrum, the refractive index at a wavelength of 550 nm of the cured product or the molded article containing the cured product is calculated from the value at a wavelength of 550 nm and the refractive index of the substrate according to the Fresnel formula (for example, the original fifth edition of Hecht Optics I, published by Maruzen Publishing Co., Ltd. in 2018, pp. 209-226). Thus, the refractive index at a wavelength of 550 nm of the cured product or the molded article containing the cured product can be obtained.

[0263] <Use Applications>

[0264] Uses as a solidified product or a molded product include, for example: glass substitutes and their surface coating materials; coating materials for window glass, daylighting glass, and light source protection glass in houses, facilities, transportation equipment, etc.; window films for houses, facilities, transportation equipment, etc.; interior and exterior decorative materials for houses, facilities, transportation equipment, etc., interior and exterior decorative coatings, and coating films formed from such coatings; alkyd resin paint coatings and coating films formed from such coatings; acrylic paint coatings and coating films formed from such coatings; components for light sources that generate ultraviolet rays such as fluorescent lamps and mercury lamps; shielding materials for electromagnetic waves generated by various displays, components for precision machinery, electronic and electrical equipment; containers or packaging materials for food, chemicals, pharmaceuticals, etc.; bottles, boxes, blister packs, cups, special packaging, optical disc coatings, agricultural or industrial plates or films; anti-fading agents for printed matter, dyed matter, dyes, pigments, etc.; protective films for polymer supports (e.g., for plastic components of mechanical and automotive parts); printed matter cover layers; inkjet medium films; matte laminated films; optical films; safety glass / front glass interlayers; electrochromic / photochromic uses; cover laminated films; solar heat control films; cosmetics such as sunscreen, shampoo, conditioner, hair styling agents, etc.; fiber products and fibers for clothing such as sportswear, socks, hats, etc.; interior household items 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 (e.g., spectacle lenses, camera lenses, and microlenses, pickup lenses described later), mirrors, photographic materials, etc.; document materials 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 encapsulation materials, etc.

[0265] The molded product is suitable for use 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 for the purpose of improving the light collection efficiency of each photoelectric conversion element can be used. Further, in the display device, a lens for the purpose of improving the light extraction efficiency from pixels can be used. The lens can be a microlens. Examples of the display device include a liquid crystal display device, an organic EL display device, etc.

[0266] As high refractive index materials, inorganic compounds such as zirconia and titanium oxide have been conventionally known. However, in the case of producing a molded product containing a high refractive index material composed of an inorganic compound, there are cases where it is difficult to perform etching and other processes and it is not easy to form, and also there are problems such as scattering of the high refractive index material during molding and resulting in contamination. Such problems can be solved by using an organic compound, i.e., the high refractive index material of the present embodiment.

[0267] The cured product of the composition of the present embodiment can suitably use a main-chain scission type positive resist. In the formation of a resist pattern using the cured product of the composition of the present embodiment, by irradiation with ionizing radiation (such as an electron beam, KrF laser, ArF laser, EUV laser, etc.), the main chain of the polymer of component (A) constituting the cured product is cut in the irradiated portion of the resist film, becoming low molecular weight. Therefore, a difference in solubility with respect to the developer is generated between the exposed portion and the unexposed portion, and a resist pattern is formed. The resist pattern using the cured product of the composition of the present embodiment can be applied when forming a resist pattern in the manufacture of printed circuit boards such as stacked substrates; semiconductors; photomasks; molds, etc.

[0268] Examples

[0269] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. It should be noted that, hereinafter, unless otherwise specified, "parts" means "parts by mass".

[0270] [Synthesis Example 1]

[0271] <Synthesis of Compound (Aa-1)>

[0272] ·Synthesis of Compound (Aa-1a)

[0273]

[0274] The inside of a four-necked flask equipped with a serpentine cooling tube and a thermometer was made into a nitrogen atmosphere, 30 parts of 1,6-naphthalenedithiol, 165 parts of acetone, 45 parts of pure water, and 139 parts of epichlorohydrin were added to the above flask, and the mixture was stirred in an ice bath for 15 minutes. Next, 15 parts of sodium hydroxide, 66 parts of acetone, and 203 parts of pure water were added to another flask and completely dissolved, and then added dropwise to the above four-necked flask over 1 hour. After the dropwise addition, the temperature was raised to 30 °C, and the mixture was stirred at 30 °C for 2 hours. The resulting mixture was purified to obtain 46 parts of the compound represented by the formula (Aa-1a).

[0275] Perform 1 H-NMR analysis and LC-MS measurement to confirm the formation of compound (Aa-1a).

[0276] 1 H-NMR (deuterochloroform) δ: 8.37 - 8.39 (1H), 7.85 (1H), 7.39 - 7.70 (4H), 3.08 - 3.29 (5H), 2.94 - 2.98 (1H), 2.57 - 2.81 (3H), 2.39 - 2.41 (1H) LC-MS: [M+H] + = 305.5

[0277] ·Synthesis of Compound (Aa-1)

[0278]

[0279] Make the inside of a four-necked flask equipped with a coiled cooling tube and a thermometer into a nitrogen atmosphere. Add 3 parts of compound (Aa-1a), 30 parts of methanol, 30 parts of toluene, 0.05 part of acetic anhydride, and 3.8 parts of thiourea to the above flask and stir at room temperature for 24 hours. Purify the resulting mixture to obtain 2.5 parts of the compound represented by formula (Aa-1).

[0280] Perform 1 H-NMR analysis and LC-MS determination to confirm the formation of compound (Aa-1).

[0281] 1 H-NMR (deuterochloroform) δ: 8.39 - 8.43 (1H), 7.86 (1H), 7.40 - 7.74 (4H), 3.40 - 3.53 (2H), 3.04 - 3.18 (2H), 2.78 - 2.96 (2H), 2.47 - 2.49 (1H), 2.35 - 2.36 (1H), 2.14 - 2.16 (1H), 1.93 - 1.94 (1H) LC-MS: [M+H] + = 337.5

[0282] [Examples 1 to 12 and Comparative Examples 1 to 4]

[0283] <Preparation of Composition>

[0284] Add the compounding ingredients shown in Table 1 in the amounts shown in Table 1 (unit: parts by mass) to a flask and stir to prepare the liquid compositions of Examples 1 to 12 and Comparative Examples 1 to 4. It was confirmed that the compositions of Examples 1 to 12 and Comparative Examples 1 to 4 were transparent to the naked eye and the compounding ingredients were uniformly dissolved.

[0285] The details of the abbreviations of the compounding ingredients shown in Table 1 are as follows.

[0286] Component (A)

[0287] · (A-1): The compound represented by formula (Aa-1) synthesized in Synthesis Example 1

[0288] Component (B)

[0289] · (B-1): The compound represented by formula (I-A)

[0290]

[0291] · (B-2): The compound represented by formula (I-B)

[0292]

[0293] ·(B - 3): The compound represented by formula (I - C)

[0294]

[0295] ·(B - 4): The compound represented by formula (I - D)

[0296]

[0297] ·(B - 5): The compound represented by formula (I - E)

[0298]

[0299] ·(B - 6): The compound represented by formula (I - F)

[0300]

[0301] ·(B - 7): The compound represented by formula (I - G)

[0302]

[0303] ·(B - 8): The compound represented by formula (II - A)

[0304]

[0305] ·(B - 9): The compound represented by formula (II - B)

[0306]

[0307] ·(B - 10): The compound represented by formula (II - C)

[0308]

[0309] (Component (b) (basic catalyst other than component (B)) · (b - 1): The compound represented by formula (b - 1)

[0310]

[0311] ·(b - 2): The compound represented by formula (b - 2)

[0312]

[0313] ·(b - 3): The compound represented by formula (b - 3)

[0314]

[0315] ·(b - 4): The compound represented by formula (b - 4)

[0316]

[0317] (C) component

[0318] · (C-1): Formic acid

[0319] (D) component

[0320] · (D-1): Cyclopentanone

[0321] <Evaluation test>

[0322] (1) Formation of cured film

[0323] About 3 mL of the compositions of Examples 1 to 12 and Comparative Examples 1 to 4 were respectively dropped onto an alkali-free glass plate (thickness 0.7 mm, manufactured by Corning, "Eagle XG"), and spin-coated under the conditions of 1000 rpm and 20 seconds using a spin coater (manufactured by MIKASA Co., Ltd., "MS-B100") to form a coating film. The alkali-free glass plate having the coating film formed thereon was heated at 60°C for 2 minutes to remove the solvent. Then, the alkali-free glass plate having the coating film formed thereon was heated at 120°C for 10 minutes as post-baking to obtain an alkali-free glass having a cured film formed thereon. The film thickness of the cured film on the alkali-free glass was measured using a stylus profilometer (manufactured by Bruker, "DekTak XT"), and as a result, the film thickness was 1.5 μm in all cases.

[0324] (2) Curing property (film thickness retention rate)

[0325] Using the alkali-free glass plate having the cured film formed thereon prepared in the above (2), the curing property (film thickness retention rate) of the composition was evaluated according to the following evaluation criteria. The curing property was evaluated by immersing the alkali-free glass plate having the cured film formed thereon in acetone at 23°C for 10 minutes, observing the change in the appearance 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 1.

[0326] 5: No change in appearance, film thickness retention rate is 95% to 100%.

[0327] 4: No change in appearance, film thickness retention rate is less than 95% and 90% or more.

[0328] 3: No change in appearance, film thickness retention rate is less than 90% and 80% or more.

[0329] 2: No change in appearance, film thickness retention rate is less than 80%.

[0330] 1: Regardless of the film thickness retention rate, the cured film became white and turbid after immersion.

[0331] (3) Heat resistance

[0332] Using the E-glass sheet formed with a cured film prepared in the above (2), the heat resistance of the composition was evaluated according to the following evaluation criteria. The heat resistance was evaluated by allowing the E-glass sheet formed with a cured film to stand on a hot plate heated to 260 °C for 5 minutes and calculating the change in transmittance at a wavelength of 450 nm of the cured film before and after heating (transmittance change = transmittance of the cured film before heating - transmittance of the cured film after heating). The results are shown in Table 1.

[0333] 5: The transmittance change is 0% or more and less than 2%.

[0334] 4: The transmittance change is 2% or more and less than 5%.

[0335] 3: The transmittance change is 5% or more and less than 10%.

[0336] 2: The transmittance change is 10% or more and less than 15%.

[0337] 1: The transmittance change is 15% or more.

[0338] (4) Storage stability

[0339] The compositions of Examples 1 to 12 and Comparative Examples 1 to 4 were respectively stored in brown bottles, and the storage stability of the compositions at room temperature (23 °C) was evaluated according to the following evaluation criteria. The results are shown in Table 1.

[0340] A: No white turbidity occurred in the composition after 120 days.

[0341] B: No white turbidity occurred in the composition after 90 days, but white turbidity occurred in the composition after 120 days.

[0342] C: No white turbidity occurred in the composition after 60 days, but white turbidity occurred in the composition after 90 days.

[0343] D: White turbidity occurred in the composition after 60 days.

[0344] [Table 1]

[0345]

[0346] As shown in Table 1, the compositions of the examples were superior to the compositions of the comparative examples in terms of curability, heat resistance, and storage stability. From these results, it was confirmed that the composition of the present invention can form a cured product having excellent storage stability, curability, and heat resistance.

Claims

1. A composition comprising: Compound A having at least one thiirane group or thietanyl group, and Compound B, which is at least one selected from a compound having a skeleton represented by formula (I) and a salt thereof and a compound having a skeleton represented by formula (II) and a salt thereof, In formula (I), R 1A represents a hydrogen atom or a hydrocarbon group which may have a substituent, In formula (II), R 2A represents a hydrocarbon group which may have a substituent or -P(=NR 2x1 )(N(R 2x2 )2)2, R 2x1 and R 2x2 Each independently represents a hydrocarbon group which may have a substituent, and a plurality of R 2x2 They can be the same or different. Each dashed line represents two single bonds or one double bond.

2. The composition according to claim 1, wherein The compound B is at least one selected from an organic carboxylate salt of a compound having a skeleton represented by formula (I) and an organic carboxylate salt of a compound having a skeleton represented by formula (II).

3. The composition according to claim 1, wherein The compound having a skeleton represented by formula (I) is a compound represented by formula (I-2), In formula (I-2), R 1A As mentioned above, R 1A Synonymous, Ring X 1A and Ring X 1B Each independently represents an aliphatic heterocycle which may have a substituent.

4. The composition according to claim 1, wherein A polymerization inhibitor C is further contained.

5. The composition according to claim 1, wherein The compound A is a compound represented by formula (A-1), In formula (A-1), L represents a single bond or a divalent group, and two Ls may be the same or different. A 1 Represents an oxygen atom or a sulfur atom, two A 1 They can be the same or different, but two A 1 At least one of is a sulfur atom, m represents 0 or 1, and two m can be the same or different. n represents any integer from 0 to 6, R 1 represents a monovalent substituent, R 1 When multiple, multiple R 1 Can be the same or different, R 2 represents a hydrogen atom or a monovalent substituent, and the two R 2 Can be the same or different.

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

7. A cured product, which is a cured product of the composition according to any one of claims 1 to 5. A display device comprising the cured product according to claim 7.

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

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