Composition, curable composition, cured product, and method for producing cured product

Abstract

To provide a composition having superior storage stability and low-temperature curability.SOLUTION: The present disclosure provides a composition comprising an imidazole-based compound including at least one selected from an imidazole compound and a modified imidazole compound, and a tertiary amine compound other than the imidazole-based compound, wherein the tertiary amine compound includes at least one selected from a first amine compound having only tertiary amino groups as amino groups, a second amine compound having both a tertiary amino group and at least one of a primary amino group and a secondary amino group, and a third amine compound which is a derivative of the second amine compound, and wherein the total content of the second amine compound among the first amine compound, second amine compound, and third amine compounds is 10 pts.mass or more and 45 pts.mass or less relative to 100 pts.mass of the total of the imidazole-based compound and the tertiary amine compound.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a composition, a curable composition, a cured product, and a method for producing the cured product.

Background Art

[0002] Epoxy compounds are used in various applications such as adhesives, paints, electrical insulating materials, composite materials, and civil engineering and construction materials. In addition, as curing agents used in curable compositions containing epoxy compounds, various curing agents such as imidazoles, amines, amine-based curing agents such as dicyandiamide, and acid anhydrides, phenols, hydrazines, guanidines, thiols, etc. are used in a wide range of applications. For example, Patent Document 1 discloses a curing agent composition in which a thiol compound and an amine-based curing agent are used in combination as curing agents.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the curing agent described in Patent Document 1 has a problem that it is difficult to simultaneously satisfy both storage stability and low-temperature curability.

[0005] The present disclosure has been made in view of the above problems, and the main object is to provide a composition that can be used as a curing agent excellent in storage stability and low-temperature curability.

Means for Solving the Problems

[0006] As a result of intensive studies, the present inventors have found that a composition excellent in storage stability and low-temperature curability can be obtained by using a predetermined amount of a tertiary amine compound in combination with an imidazole-based compound.

[0007] That is, the present disclosure provides a composition containing at least one imidazole-based compound including an imidazole compound and a modified imidazole compound, and a tertiary amine compound other than the imidazole-based compound, wherein the tertiary amine compound contains at least one selected from a first amine compound having only a tertiary amino group as an amino group, a second amine compound having a tertiary amino group and at least one of a primary amino group and a secondary amino group, and a third amine compound which is a derivative of the second amine compound, and the total content of the second amine compound constituting the first amine compound, the second amine compound, and the third amine compound is 10 parts by mass or more and 45 parts by mass or less in 100 parts by mass in total of the imidazole-based compound and the tertiary amine compound.

[0008] According to the present disclosure, by using a predetermined amount of a tertiary amine compound in combination with an imidazole-based compound, it can be used as a curing agent excellent in storage stability and low-temperature curability.

[0009] In the present disclosure, it is preferable that the total content of the second amine compound constituting the first amine compound, the second amine compound, and the third amine compound is 5 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. This is because the composition can be used as a curing agent excellent in the balance between storage stability and low-temperature curability.

[0010] In the present disclosure, it is preferable that the imidazole-based compound contains a modified imidazole compound. This is because the composition can be used as a curing agent excellent in the balance between storage stability and low-temperature curability.

[0011] In the present disclosure, it is preferable that the tertiary amino group contains a dihydrocarbon amino group. This is because the composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0012] In the present disclosure, it is preferable that the number of the dihydrocarbon amino groups is 1 or more and 5 or less in the tertiary amine compound. This is because the composition becomes more excellent in low-temperature curability and storage stability.

[0013] In the present disclosure, it is preferable that the second amine compound constituting the first amine compound, the second amine compound, and the third amine compound contains an aliphatic compound. This is because the composition becomes more excellent in low-temperature curability and storage stability.

[0014] In the present disclosure, it is preferable that the third amine compound is a reaction product of the second amine compound and an epoxy compound. This is because the composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0015] In the present disclosure, it is preferable that the composition contains a phenol resin. This is because the composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0016] In the present disclosure, bisphenol A may be contained in the composition. This is because the composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0017] In the present disclosure, it is preferable that the content of bisphenol A is 1 ppm or more and 30,000 ppm or less with respect to the total of the imidazole-based compound and the tertiary amine compound. This is because the composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0018] The present disclosure provides a composition containing at least one imidazole-based compound including at least one of an imidazole compound and a modified imidazole compound, a tertiary amine compound other than the above imidazole-based compound, and a thiol compound, wherein the tertiary amine compound contains at least one selected from a first amine compound having only a tertiary amino group as an amino group, a second amine compound having a tertiary amino group and at least one of a primary amino group and a secondary amino group, and a third amine compound which is a derivative of the second amine compound, and the total content of the second amine compound constituting the first amine compound, the second amine compound, and the third amine compound is 10 parts by mass or more and 45 parts by mass or less in 100 parts by mass in total of the imidazole-based compound and the tertiary amine compound.

[0019] According to the present disclosure, by having the above imidazole-based compound, tertiary amine compound, and thiol compound, it can be used as a curing agent excellent in storage stability and low-temperature curability.

[0020] The present disclosure provides a curable composition containing at least one imidazole-based compound including at least one of an imidazole compound and a modified imidazole compound, a tertiary amine compound other than the above imidazole-based compound, and a curable compound, wherein the tertiary amine compound contains at least one selected from a first amine compound having only a tertiary amino group as an amino group, a second amine compound having a tertiary amino group and at least one of a primary amino group and a secondary amino group, and a third amine compound which is a derivative of the second amine compound, and the total content of the second amine compound constituting the first amine compound, the second amine compound, and the third amine compound is 10 parts by mass or more and 45 parts by mass or less in 100 parts by mass in total of the imidazole-based compound and the tertiary amine compound.

[0021] According to the present disclosure, by having an imidazole-based compound and a predetermined amount of a tertiary amine compound, it becomes excellent in low-temperature curability and storage stability.

[0022] In the present disclosure, it is preferable that the curable composition contains a thiol compound. This is because the curable composition can more effectively exhibit the effect of being excellent in storage stability and low-temperature curability.

[0023] The present disclosure provides a cured product of the above-described curable composition. According to the present disclosure, by using the above-described curable composition, it is easy to form a cured product, and the cured product has excellent quality stability.

[0024] In the present disclosure, there is provided a method for producing a cured product, which is characterized by having a heating step of heating the above-described curable composition. According to the present disclosure, by using the above-described curable composition, it is easy to form a cured product, and it is easy to produce a cured product having excellent quality stability.

Effects of the Invention

[0025] According to the present disclosure, it is possible to provide a composition that can be used as a curing agent excellent in storage stability and low-temperature curability.

Modes for Carrying Out the Invention

[0026] The present disclosure relates to a composition, a curable composition, a cured product, and a method for producing a cured product. Hereinafter, the composition, curable composition, cured product, and method for producing a cured product of the present disclosure will be described in detail.

[0027] A. Composition First, the composition of the present disclosure will be described. The composition of the present disclosure is a composition containing an imidazole-based compound and a tertiary amine compound other than the above imidazole-based compound, wherein the tertiary amine compound is a first amine compound having only a tertiary amino group as an amino group, a second amine compound having a tertiary amino group and at least one of a primary amino group or a secondary amino group, and a third amine compound which is a derivative of the second amine compound, and contains at least one selected from the group consisting of, and the total content of the first amine compound, the second amine compound, and the second amine compound constituting the third amine compound is 10 parts by mass or more and 45 parts by mass or less in 100 parts by mass in total of the imidazole-based compound and the tertiary amine compound.

[0028] According to the present disclosure, by using a predetermined amount of a tertiary amine compound in combination with an imidazole-based compound, it can be used as a curing agent excellent in storage stability and low-temperature curability. Here, the reason for obtaining the above-described effects is not clear, but it is presumed as follows.

[0029] That is, by using a predetermined amount of a tertiary amine compound in combination with an imidazole-based compound, each curing system can act independently and affect each other, so that the effect of accelerating curing can be effectively exerted. As a result, by containing an imidazole-based compound and a predetermined amount of a tertiary amine compound, it can be used as a curing agent excellent in low-temperature curability. In particular, when a thiol compound is used in combination, due to the high basicity of the tertiary amine compound, the reactivity with the thiol compound is improved compared to the imidazole-based compound alone, so that it can be used as a curing agent excellent in low-temperature curability. In addition, when having low-temperature curability, usually, the storage stability tends to decrease, but when combined with a predetermined amount of a tertiary amine compound, as a result of the imidazole-based compound functioning as a stabilizer for the tertiary amine compound, the storage stability can also be made excellent.

[0030] Therefore, the above composition is excellent in low-temperature curability and storage stability, and can more efficiently exhibit the effect of being excellent in low-temperature curability and storage stability, especially when used in combination with a thiol compound.

[0031] The composition of the present disclosure contains an imidazole-based compound and a tertiary amine compound. Hereinafter, each component of the composition of the present disclosure will be described in detail.

[0032] 1. Imidazole-based compound The imidazole-based compound is a compound having an imidazole ring structure. As such an imidazole-based compound, for example, a compound generally used as an anionic curing agent such as a curing agent for an epoxy compound can be used. Examples of the imidazole-based compound include an imidazole compound and a modified imidazole compound which is a derivative of the imidazole compound. In the present disclosure, the imidazole-based compound can include at least one of an imidazole compound and a modified imidazole compound, preferably includes a modified imidazole compound, and more preferably includes both an imidazole compound and a modified imidazole compound. This is because the above composition can be used as a curing agent excellent in the balance between storage stability and low-temperature curability. Further, when a reaction product of an imidazole compound and an epoxy compound is used as the modified imidazole, it has the advantage that it is easy to reduce the content of bisphenol A.

[0033] (1) Imidazole compound The imidazole compound can be a compound having no thiol group, epoxy group, etc. Examples of such an imidazole compound include an aliphatic imidazole compound having no heterocyclic ring other than an aromatic hydrocarbon ring and an imidazole ring, and an aromatic imidazole compound having an aromatic hydrocarbon ring and no heterocyclic ring other than an imidazole ring.

[0034] Examples of the aliphatic imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-isopropylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-aminopropylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-butoxycarbonylethyl-2-methylimidazole, 1-butoxycarbonylethyl-2-ethyl-4-methylimidazole, 1-(2-ethylhexyl)carbonylethyl-2-methylimidazole, 1-(2-ethylhexyl)carbonylethyl-2-ethyl-4-methylimidazole, 1-octyloxycarbonylethyl-2-methylimidazole, 1-octyloxycarbonylethyl-2-ethyl-4-methylimidazole, hexanediol bis(2-methylimidazolylethanoic acid) ester, hexanediol bis(2-ethyl-4-methylimidazolylethanoic acid) ester, decanediol bis(2-methylimidazolylethanoic acid) ester, decanediol bis(2-ethyl-4-methylimidazolylethanoic acid) ester, tricyclopentanedimethanol bis(2-methylimidazolylethanoic acid) ester, tricyclopentanedimethanol bis(2-ethyl-4-methylimidazolylethanoic acid) ester, imidazole silane (e.g., manufactured by Shikoku Chemicals Corporation; 2MUSIZ), and the like.

[0035] Examples of the aromatic imidazole compound include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-phenylmethyl-2-imidazole, 1-phenylmethyl-2-ethyl-4-methylimidazole, 1-phenylmethyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-butoxycarbonylethyl-2-phenylimidazole, 1-(2-ethylhexyl)carbonylethyl-2-phenylimidazole, 1-octyloxycarbonylethyl-2-phenylimidazole, hexanediol bis(2-phenylimidazolylethanoic acid) ester, decanediol bis(2-phenylimidazolylethanoic acid) ester, tricyclopentanedimethanol bis(2-phenylimidazolylethanoic acid) ester, 1-(2-hydroxynaphthylmethyl)-2-methylimidazole, 1-(2-hydroxynaphthylmethyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxynaphthylmethyl)-2-phenylimidazole, and the like.

[0036] Examples of commercially available products of the imidazole compound include 2P4MHZ, 2PHZ-PW, 2E4MZ-A, 2MZ-A, 2MA-OK, 2PZ-CN, 2PZCNS-PW, C11Z-CN, and C11Z-A (manufactured by Shikoku Kasei Kogyo Co., Ltd., etc.).

[0037] The molecular weight of the imidazole compound is not particularly limited as long as the effects of the present disclosure can be exhibited. For example, it is preferably 60 or more and 300 or less, more preferably 70 or more and 200 or less, and even more preferably 80 or more and 150 or less. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0038] In the present disclosure, it is preferable that the imidazole compound is a compound represented by the following formula (1). This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0039] [ka]

[0040] (In the formula, R 1 ~R 4 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms which may have a substituent.

[0041] R 1 ~R 4 The aliphatic hydrocarbon group having 1 to 20 carbon atoms used in may be a hydrocarbon group that does not contain an aromatic hydrocarbon ring or a heterocycle, and examples thereof include chain aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aliphatic ring-containing groups having 3 to 20 carbon atoms. Examples of the chain aliphatic hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms. Examples of the aliphatic ring-containing group having 3 to 20 carbon atoms include a cycloalkyl group having 3 to 20 carbon atoms and a cycloalkylalkyl group having 4 to 20 carbon atoms.

[0042] The alkyl group having 1 to 20 carbon atoms may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, iso-amyl, tert-amyl, hexyl, heptyl, and octyl. Examples of branched alkyl groups include iso-propyl, sec-butyl, tert-butyl, iso-butyl, iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, iso-octyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebrotadecyl, and octadecyl.

[0043] The alkenyl group having 2 to 20 carbon atoms may be linear or branched. It may also be a terminal alkenyl group having an unsaturated bond at the terminal or an internal alkenyl group having an unsaturated bond inside. Examples of the terminal alkenyl group include vinyl group, allyl group, 2-methyl-2-propenyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, and the like. Examples of the internal alkenyl group include 2-butenyl group, 3-pentenyl group, 2-hexenyl group, 3-hexenyl group, 2-heptenyl group, 3-heptenyl group, 4-heptenyl group, 3-octenyl group, 3-nonenyl group, 4-decenyl group, 3-undecenyl group, 4-dodecenyl group, 4,8,12-tetradecatrienyl allyl group, and the like.

[0044] Examples of the cycloalkyl group having 3 to 20 carbon atoms include a saturated monocyclic alkyl group having 3 to 20 carbon atoms, a saturated polycyclic alkyl group having 3 to 20 carbon atoms, and a group having 4 to 20 carbon atoms in which one or more hydrogen atoms in the ring of these groups are substituted with an alkyl group. Examples of the saturated monocyclic alkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, and the like. Examples of the saturated polycyclic alkyl group include adamantyl group, decahydronaphthyl group, octahydropentalene group, bicyclo[1.1.1]pentanyl group, and the like. Examples of the alkyl group that substitutes the hydrogen atom in the ring of the saturated monocyclic or saturated polycyclic alkyl group include the groups exemplified as the alkyl group having 1 to 20 carbon atoms above. Examples of the group in which one or more hydrogen atoms in the ring of the saturated polycyclic alkyl group are substituted with an alkyl group include bornyl group, and the like.

[0045] The cycloalkylalkyl group having 4 to 20 carbon atoms as described above means a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with a cycloalkyl group. The cycloalkyl group in the cycloalkylalkyl group may be a monocyclic group or a polycyclic group. Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms in which the cycloalkyl group is monocyclic include a cyclopropylmethyl group, a 2-cyclobutylethyl group, a 3-cyclopentylpropyl group, a 4-cyclohexylbutyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, a 2-cyclononylethyl group, and a 2-cyclodecylethyl group. Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms in which the cycloalkyl group is polycyclic include a 3-3-adamantylpropyl group and a decahydronaphthylpropyl group.

[0046] R 1 ~R 4 The aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms used for R~R is a hydrocarbon group that contains an aromatic hydrocarbon ring and does not contain a heterocyclic ring, and may have an aliphatic hydrocarbon structure. Examples of such an aromatic hydrocarbon ring-containing group include an aryl group having 6 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms.

[0047] The aryl group having 6 to 20 carbon atoms as described above may have a monocyclic structure, a condensed ring structure, or may be one in which two aromatic hydrocarbon rings are linked. The aryl group in which two aromatic hydrocarbon rings are linked may be one in which two monocyclic aromatic hydrocarbon rings are linked, one in which a monocyclic aromatic hydrocarbon ring and a condensed ring aromatic hydrocarbon ring are linked, or one in which two condensed ring aromatic hydrocarbon rings are linked. The linking group for linking two aromatic hydrocarbon rings may be any group as long as the entire aryl group has aromaticity, and examples include a single bond, a sulfide group (-S-), and a carbonyl group.

[0048] The aryl group includes not only a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring (hereinafter, may also be referred to as an aromatic ring group), but also a group in which one or more of the hydrogen atoms in the aromatic ring group are substituted with a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 15 carbon atoms. Examples of the aryl group having a monocyclic structure include a phenyl group; an alkylphenyl group such as a tolyl group, a xylyl group, an ethylphenyl group, and a 2,4,6-trimethylphenyl group; and the like. Examples of the aryl group having a condensed ring structure include a naphthyl group, an anthracenyl group, a phenanthryl group, and a pyrenyl group. Examples of the aryl group in which two monocyclic aromatic hydrocarbon rings are linked include a biphenyl group, a diphenyl sulfide group, and a benzoyl phenyl group.

[0049] The arylalkyl group having 7 to 20 carbon atoms means a group in which one or more of the hydrogen atoms in the alkyl group are substituted with an aryl group. Examples of the arylalkyl group having 7 to 20 carbon atoms include a benzyl group, a fluorenyl group, an indenyl group, a 9-fluorenylmethyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, and a naphthylpropyl group.

[0050] Examples of the substituent used for the aliphatic hydrocarbon group and the aromatic hydrocarbon ring-containing group include a group or atom that substitutes the hydrogen atom in the aliphatic hydrocarbon group and the aromatic hydrocarbon ring-containing group, and examples thereof include a halogen atom, a nitrile group, and an amino group (-NH2). Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom.

[0051] In the present disclosure, R 1is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, still more preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0052] In the present disclosure, R 2 and R 3 are each independently preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and still more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. This is because the above composition becomes excellent in low-temperature curability and storage stability. In the present disclosure, R 4 is preferably a hydrogen atom. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0053] In the present disclosure, the imidazole compound is preferably an aliphatic imidazole compound. In the above formula (1), R 1 is an alkyl group having 1 to 4 carbon atoms, R 2 and R 3 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and it is more preferable that R 4 is a hydrogen atom. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0054] In the present disclosure, it is preferable that the imidazole compound includes 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, more preferably includes 2-methylimidazole and 2-ethyl-4-methylimidazole, and even more preferably includes 2-ethyl-4-methylimidazole. This is because the composition becomes excellent in low-temperature curability and storage stability. Further, it has the advantage that it is easy to reduce the content of bisphenol A during the production of the modified imidazole.

[0055] When the imidazole-based compound includes both an imidazole compound and a modified imidazole compound, the content of the imidazole compound is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 20 parts by mass or less, and even more preferably 5 parts by mass or more and 15 parts by mass or less in 100 parts by mass of the imidazole-based compound, that is, in a total of 100 parts by mass of the imidazole compound and the modified imidazole compound. This is because the composition becomes excellent in low-temperature curability and storage stability.

[0056] When the imidazole-based compound includes both an imidazole compound and a modified imidazole compound, the content of the imidazole compound is preferably 0.01 mol or more and 4.0 mol or less, more preferably 0.1 mol or more and 3.0 mol or less, even more preferably 0.3 mol or more and 1 mol or less, and particularly preferably 0.4 mol or more and 0.8 mol or less with respect to 1 mol of the modified imidazole compound. This is because the composition becomes excellent in low-temperature curability and storage stability.

[0057] (2) Modified imidazole compound The above-mentioned modified imidazole compound is a derivative of an imidazole compound. Examples of such modified imidazole compounds include imidazole compounds obtained by reacting an amino group in an imidazole compound with a carboxylic acid, an epoxy compound, an isocyanate compound, urea, etc. More specifically, examples include imidazole compounds obtained by reacting a primary amino group or a secondary amino group in an imidazole compound with a carboxylic acid, an epoxy compound, an isocyanate compound, urea, etc.

[0058] In the present disclosure, among others, an imidazole compound obtained by reacting an amino group in the imidazole ring of an imidazole compound with a carboxylic acid, an epoxy compound, an isocyanate compound, urea, etc. is preferable. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability. More specifically, examples of the above reaction include dehydration condensation with a carboxylic acid, addition reaction with an epoxy compound, addition reaction with an isocyanate compound, Michael addition reaction, Mannich reaction, condensation reaction with urea, and condensation reaction with a ketone; etc. In the present disclosure, it is preferable that the above modified imidazole compound contains a reaction product of an imidazole compound and an epoxy compound. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0059] Examples of the carboxylic acid, isocyanate compound, etc. used for the formation of the above modified imidazole include the content described in International Publication No. 2023 / 074450.

[0060] Examples of the epoxy compound used for forming the modified imidazole include monoglycidyl ether compounds, monoglycidyl ester compounds, polyglycidyl ether compounds of mononuclear polyhydric phenol compounds, polynuclear polyhydric phenol compounds or polyglycidyl ether compounds of alkylene oxide adducts of the polynuclear polyhydric phenol compounds, polyglycidyl ethers of polyhydric alcohols, glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids, homopolymers or copolymers of glycidyl methacrylate, epoxy compounds having glycidylamino groups, epoxidized products of cyclic olefin compounds, epoxidized conjugated diene polymers, heterocyclic compounds, and the like.

[0061] Examples of the polynuclear polyhydric phenol compounds include compounds having a naphthalene structure, compounds having a biphenyl structure, compounds having a bisphenol structure, and novolak-type phenol resins. Examples of the compounds having a naphthalene structure include dihydroxynaphthalene. Examples of the compounds having a biphenyl structure include biphenyl.

[0062] Examples of the compound having the bisphenol structure include, as a compound in which two hydroxyphenyl groups are bonded by one atom, methylene bisphenol (bisphenol F), methylene bis(ortho-cresol); ethylidene bisphenol; isopropylidene bisphenol (bisphenol A), isopropylidene bis(ortho-cresol), compounds having a bisphenol A structure such as tetrabromobisphenol A; 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, and oxybisphenol. "Two hydroxyphenyl groups are bonded by one atom" means that the bond chain length of the linking group connecting the benzene rings of the two hydroxyphenyl groups is one atom. The bisphenol A structure refers to a structure in which two hydroxyphenyl groups are bonded by an isopropylidene group between the benzene rings, and polyglycidyl ether compounds of polyhydric phenol compounds having this structure include so-called bisphenol A type epoxy resins. Examples of the compound having a bisphenol structure in which two hydroxyphenyl groups are bonded by two or more atoms include 1,3-bis(4-hydroxytumylbenzene) and 1,4-bis(4-hydroxytumylbenzene).

[0063] Examples of the novolak type phenol resin include phenol novolak, ortho-cresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinol novolak, and terpene phenol. Examples of the alkylene oxide constituting the alkylene oxide adduct of the above-mentioned polynuclear polyhydric phenol compound include ethylene oxide, propylene oxide, and the like.

[0064] Examples of the monoglycidyl ether compound include monoglycidyl ether compounds such as phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, sec-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, and stearyl glycidyl ether; and glycidyl esters such as versatic acid glycidyl ester. The above-mentioned mononuclear polyhydric phenol compound can be a compound having one aromatic hydrocarbon ring and two or more phenolic hydroxyl groups, and examples thereof include hydroquinone, resorcinol, pyrocatechol, and phloroglucinol.

[0065] Examples of the above-mentioned polyhydric alcohols include compounds having no aromatic hydrocarbon ring, such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, and sorbitol. Examples of the aliphatic, aromatic or alicyclic polybasic acids that constitute the homopolymers or copolymers of the glycidyl esters of the above-mentioned aliphatic, aromatic or alicyclic polybasic acids and glycidyl methacrylate include maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and endomethylenetetrahydrophthalic acid.

[0066] Examples of the epoxy compound having the above-mentioned glycidylamino group include N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, and diglycidyl orthotoluidine. Examples of the epoxidized product of the above cyclic olefin compound include vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, and the like. Examples of the epoxidized conjugated diene polymer include epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, and the like. Examples of the above heterocyclic compound include triglycidyl isocyanurate and the like.

[0067] Examples of commercially available products of the above modified imidazole compound include Adeka Hardener EH-5011S and Adeka Hardener EH-5046S manufactured by ADEKA CORPORATION.

[0068] In the present disclosure, it is preferable that the above epoxy compound includes a polyglycidyl ether compound of a polynuclear polyhydric phenol compound or its alkylene oxide adduct, and a polyglycidyl ether of polyhydric alcohols. More preferably, it includes a polyglycidyl ether compound of a polynuclear polyhydric phenol compound or its alkylene oxide adduct. Still more preferably, it includes a polyglycidyl ether compound of a polynuclear polyhydric phenol compound. Even more preferably, it includes a bisphenol-type epoxy compound which is a polyglycidyl ether compound of a bisphenol compound. Particularly preferably, it includes a bisphenol A-type epoxy compound which is a polyglycidyl ether compound of bisphenol A. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability. Further, when the above imidazole-based compound includes both an imidazole compound and a modified imidazole compound, the effect of reducing the content of bisphenol A can be more efficiently exhibited.

[0069] Regarding the imidazole compound constituting the above-mentioned modified imidazole compound, it can be the same as the content described in the section of the above-mentioned "(1) Imidazole compound". In the present disclosure, when the above-mentioned imidazole-based compound contains both an imidazole compound and a modified imidazole compound, the imidazole compounds constituting the above-mentioned imidazole compound and the modified imidazole compound may be the same compound or different compounds, but it is preferably the same compound. This is because the production of the above composition becomes easy.

[0070] When the above-mentioned imidazole-based compound contains both an imidazole compound and a modified imidazole compound, the content of the above-mentioned modified imidazole compound is preferably 50 parts by mass or more and 100 parts by mass or less, more preferably 70 parts by mass or more and 98 parts by mass or less, still more preferably 80 parts by mass or more and 95 parts by mass or less, and particularly preferably 85 parts by mass or more and 95 parts by mass or less in 100 parts by mass of the above-mentioned imidazole-based compound, that is, in a total of 100 parts by mass of the imidazole compound and the modified imidazole compound. This is because the above composition becomes more excellent in low-temperature curability and storage stability.

[0071] (3) Others The content of the above-mentioned imidazole-based compound is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, still more preferably 20 parts by mass or more and 45 parts by mass or less, and particularly preferably 30 parts by mass or more and 40 parts by mass or less in 100 parts by mass of the above composition. This is because the above composition becomes more excellent in low-temperature curability and storage stability.

[0072] The content of the above imidazole-based compound is preferably 1 to 99 parts by mass, more preferably 10 to 98 parts by mass, still more preferably 30 to 95 parts by mass, still more preferably 50 to 90 parts by mass, still more preferably 60 to 85 parts by mass, and particularly preferably 65 to 80 parts by mass in a total of 100 parts by mass of the above imidazole-based compound and the tertiary amine compound. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0073] The total content of the above tertiary amine compound and the above imidazole-based compound is more preferably 10 to 90 parts by mass, still more preferably 20 to 80 parts by mass, still more preferably 30 to 70 parts by mass, still more preferably 40 to 60 parts by mass, and particularly preferably 45 to 55 parts by mass in 100 parts by mass of the above composition. This is because the above composition can be used as a curing agent excellent in the balance between storage stability and low-temperature curability.

[0074] 2. Tertiary amine compound The above tertiary amine compound is a compound other than the above imidazole-based compound. Further, the above tertiary amine compound contains at least one selected from a first amine compound having only a tertiary amino group as an amino group, a second amine compound having a tertiary amino group and at least one of a primary amino group and a secondary amino group, and a third amine compound which is a derivative of the above second amine compound. Here, being other than the imidazole-based compound means a compound having no imidazole ring. Further, the above tertiary amine compound can be one having no thiol group, epoxy group, etc.

[0075] In the present disclosure, the tertiary amino group of the above tertiary amine compound refers to a structure in which three bonds of the nitrogen atom are covalently bonded to the carbon atoms of the hydrocarbon group. Therefore, when the carbon atom to which the nitrogen atom is bonded is the carbon atom constituting the carbonyl group, that is, when an amide group is formed together with the nitrogen atom, it does not correspond to the tertiary amino group. Examples of such a tertiary amino group include a dihydrocarbon amino group, a pyridine ring, a quinuclidine ring, a group in which a nitrogen atom constitutes a nitrogen-containing heterocyclic ring such as a triethylenediamine ring, and a group in which a nitrogen atom is bonded to two or more groups selected from a dihydrocarbon amino group and a nitrogen-containing heterocyclic group.

[0076] In the present disclosure, it is preferable that the above tertiary amino group contains a dihydrocarbon amino group. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability. Here, the dihydrocarbon amino group means a group in which the nitrogen atom constituting the tertiary amino group is bonded to two hydrocarbon groups, and does not constitute a nitrogen-containing heterocyclic ring. Such a dihydrocarbon amino group can be, for example, a group represented by the following general formula (2).

[0077] *―NR 11 R 12 (2) (In the formula, R 11 and R 12 are each an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, and R 11 and R 12 do not combine to form a nitrogen-containing heterocyclic ring. * represents the bonding position.)

[0078] Regarding the content of the aliphatic hydrocarbon group having 1 to 20 carbon atoms and the aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms used for the above R 11 and R 12 , the same content as that listed as the group used for R1 to R4 in the above general formula (1) can be adopted.

[0079] In the present disclosure, the hydrocarbon group used for R 11 and R 12 is preferably an aliphatic hydrocarbon group, that is, the dihydrocarbon amino group is preferably a dialiphatic hydrocarbon amino group, more preferably a chain aliphatic hydrocarbon group, that is, the dihydrocarbon amino group is a dicyclic aliphatic hydrocarbon amino group, and particularly preferably an alkyl group, that is, the above dihydrocarbon amino group is a dialkylamino group. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability. When the hydrocarbon group used for the above R 11 and R 12 is an alkyl group, it may be a linear alkyl group or a branched alkyl group, but a linear alkyl group is preferred. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0080] In the present disclosure, the number of carbon atoms of R 11 and R 12 is preferably independently 1 or more and 10 or less, more preferably 1 or more and 5 or less, still more preferably 1 or more and 3 or less, and particularly preferably 1 or 2, that is, a dimethylamino group or a diethylamino group, and particularly preferably 1, that is, a dimethylamino group. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0081] The number of the above dihydrocarbon amino groups is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, particularly preferably 1 or more and 2 or less, and particularly preferably 2 in the above tertiary amine compound. This is because the above composition becomes more excellent in low-temperature curability and storage stability. The above-mentioned dihydrocarbon amino group is a group in which two groups bonded to the nitrogen atom constituting the tertiary amino group are hydrocarbon groups as described above. For example, tetramethylethylenediamine and N,N,N’,N”,N”-pentamethyldiethylenetriamine have two such groups, triethylamine, N,N-dimethylaminoethylamine, and N,N-dimethylaminopyridine have one such group, and triethylenediamine has zero such groups.

[0082] The number of the above-mentioned tertiary amino groups is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, still more preferably 2 or more and 3 or less, and particularly preferably 2 in the above-mentioned tertiary amine compound. This is because the above composition becomes excellent in low-temperature curability and storage stability. Note that the number of amino groups can be the number of nitrogen atoms constituting the tertiary amino group. For example, N,N,N’,N”,N”-pentamethyldiethylenetriamine has 3 amino groups, and tetramethylethylenediamine, N,N-dimethylaminopyridine, triethylenediamine, etc. have 2 amino groups.

[0083] In the present disclosure, the above-mentioned second amine compound constituting the above-mentioned first amine compound, the above-mentioned second amine compound, and the above-mentioned third amine compound may include at least one of an aliphatic compound having no aromatic hydrocarbon ring and no nitrogen-containing heterocyclic ring, an aromatic compound having an aromatic hydrocarbon ring and no nitrogen-containing heterocyclic ring, and a heterocyclic compound having a nitrogen-containing heterocyclic ring. In the present disclosure, it is preferable that the above-mentioned second amine compound constituting the above-mentioned first amine compound, the above-mentioned second amine compound, and the above-mentioned third amine compound is an aliphatic compound or a heterocyclic compound, and more preferably an aliphatic compound. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0084] In the present disclosure, it is preferable that the above tertiary amine compound is at least one selected from the first amine compound and the third amine compound, and more preferably the first amine compound. This is because the above composition will be excellent in low-temperature curability and storage stability.

[0085] (1) First amine compound The above first amine compound may be any compound having only a tertiary amino group as an amino group. For example, aliphatic amine compounds (hereinafter sometimes referred to as first aliphatic amine compounds), aromatic amine compounds (hereinafter sometimes referred to as first aromatic amine compounds), heterocyclic amine compounds (hereinafter sometimes referred to as first heterocyclic amine compounds), etc. can be mentioned.

[0086] The molecular weight of the above first amine compound is preferably 50 or more and 500 or less, more preferably 80 or more and 300 or less, and still more preferably 100 or more and 200 or less. This is because the above composition will be excellent in low-temperature curability and storage stability.

[0087] The above first aliphatic amine compound can be a compound having no aromatic hydrocarbon ring and nitrogen-containing heterocyclic ring. For example, chain aliphatic amine compounds having no aromatic hydrocarbon ring such as triethylamine, tripropylamine, tributylamine, triamylamine, N,N-dimethylamine, N,N-dimethyllaurylamine, bis(2-dimethylaminoethyl) ether, ethyldiisopropylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylhexanediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyldipropylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine; alicyclic amine compounds having an aromatic hydrocarbon ring such as dimethylcyclohexylamine; etc. can be mentioned.

[0088] As the above-mentioned first aromatic amine compound, it can have an aromatic hydrocarbon ring and no nitrogen-containing heterocyclic ring. For example, N,N-dimethylaniline, N,N-diethylaniline, N-methyl-N-ethylaniline, N,N-benzylmethylaminoethylamine, N,N,N',N'-tetramethylphenylenediamine, methylenebis(N,N-dimethylaniline), N,N,N' N'-tetramethylxylylenediamine, etc. can be mentioned.

[0089] As the above-mentioned first heterocyclic amine compound, it only needs to have a nitrogen-containing heterocyclic ring. For example, N,N-dimethylaminopyridine, N-methylmorpholine, N-ethylmorpholine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N-methylpiperidine, quinuclidine, N,N'-dimethylpiperazine, triethylenediamine, bis(2-morpholinoethyl)ether, hexahydro-1,3,5-tris(3-dimethylaminopropyl)-1,3,5-triazine, hexamethylenetetramine, etc. can be mentioned.

[0090] In the present disclosure, the number of tertiary amino groups of the above-mentioned first amine compound only needs to be 1 or more, but is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, still more preferably 1 or more and 3 or less, still more preferably 2 or more and 3 or less, and particularly preferably 2. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0091] In the present disclosure, the number of dihydrocarbon amino groups of the above-mentioned first amine compound as a tertiary amino group is preferably 1 or more, more preferably 1 or more and 5 or less, still more preferably 1 or more and 4 or less, still more preferably 1 or more and 3 or less, still more preferably 1 or more and 2 or less, and particularly preferably 2. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0092] In the present disclosure, the number of the dihydrocarbon amino groups in the first amine compound is preferably 10% or more, more preferably 50% or more, still more preferably 80% or more, still more preferably 90% or more, and particularly preferably 100% in 100 of the number of the tertiary amino groups in the first amine compound, that is, the first amine compound has only dihydrocarbon amino groups as the tertiary amino groups. This is because the composition becomes excellent in low-temperature curability and storage stability.

[0093] In the present disclosure, the first amine compound preferably contains a first aliphatic amine compound and a first heterocyclic amine compound, and more preferably contains a first aliphatic amine compound. This is because the composition becomes excellent in low-temperature curability and storage stability.

[0094] As the above-mentioned first aliphatic amine compound, it is preferably a chain aliphatic amine compound, and preferably includes bis(2-dimethylaminoethyl) ether, ethyldiisopropylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylhexanediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyldipropylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetraamine, etc. More preferably, it includes bis(2-dimethylaminoethyl) ether, ethyldiisopropylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylhexanediamine, etc. Even more preferably, it includes bis(2-dimethylaminoethyl) ether, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylhexanediamine, etc. Particularly preferably, it includes N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylhexanediamine, etc. This is because the above composition is excellent in low-temperature curability and storage stability.

[0095] As the above-mentioned first complex cyclic amine compound, it is preferable to include a compound having two or more tertiary amino groups. More preferably, it includes N,N-dimethylaminopyridine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N-methylpiperidine, N,N'-dimethylpiperazine, triethylenediamine, bis(2-morpholinoethyl)ether, hexahydro-1,3,5-tris(3-dimethylaminopropyl)-1,3,5-triazine, and hexamethylenetetramine. Even more preferably, it includes N,N-dimethylaminopyridine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N-methylpiperidine, N,N'-dimethylpiperazine, triethylenediamine, and bis(2-morpholinoethyl)ether. Particularly preferably, it includes N,N-dimethylaminopyridine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N-methylpiperidine, and N,N'-dimethylpiperazine. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0096] (2) Second amine compound As the above-mentioned second amine compound, it may be any compound having at least one of a primary amino group or a secondary amino group together with a tertiary amino group. For example, it includes aliphatic amine compounds (hereinafter sometimes referred to as second aliphatic amine compounds), aromatic amine compounds (hereinafter sometimes referred to as second aromatic amine compounds), nitrogen-containing heterocyclic amine compounds (hereinafter sometimes referred to as second nitrogen-containing heterocyclic amine compounds), and the like.

[0097] The molecular weight of the above-mentioned second amine compound is preferably 50 or more and 500 or less, more preferably 80 or more and 300 or less, and even more preferably 100 or more and 200 or less. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0098] The above-mentioned second aliphatic amine compound can have an aromatic hydrocarbon ring and no nitrogen-containing heterocyclic ring. For example, Chain aliphatic amine compounds without an aliphatic hydrocarbon ring such as N,N-dimethylaminoethylamine, N,N-diethylaminoethylamine, N,N-diisopropylaminoethylamine, N,N-diallylaminoethylamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-diisopropylaminopropylamine, N,N-diallylaminopropylamine, N,N,N'-trimethylethylenediamine, N'-ethyl-N,N-dimethylethylenediamine, N'-ethyl-N,N-dimethylpropanediamine, N,N-(bisaminopropyl)-N-methylamine, N,N-bisaminopropylethylamine, N,N-bisaminopropylpropylamine, N,N-bisaminopropylbutylamine, N,N-bisaminopropylpentylamine, N,N-bisaminopropylhexylamine, N,N-bisaminopropyl-2-ethylhexylamine, N,N-bisaminopropylallylamine, bis[3-(N,N-dimethylaminopropyl)]amine, bis[3-(N,N-diethylaminopropyl)]amine, bis[3-(N,N-diisopropylaminopropyl)]amine, bis[3-(N,N-dibutylaminopropyl)]amine, N,N,N',N'-tetramethylguanidine; alicyclic aliphatic amine compounds having an aliphatic hydrocarbon ring such as N,N-cyclohexylmethylaminoethylamine, N,N-dicyclohexylaminoethylamine, N,N-cyclohexylmethylaminopropylamine, N,N-dicyclohexylaminopropylamine, N,N-bisaminopropylcyclohexylamine; etc. are mentioned.

[0099] As the second aromatic amine compound, a compound having an aromatic hydrocarbon ring and not having a nitrogen-containing heterocyclic ring can be used. For example, N,N-benzylmethylaminoethylamine, N,N-dibenzylaminoethylamine, N,N-benzylmethylaminopropylamine, N,N-dibenzylaminopropylamine, 4-(N,N-dimethylamino)benzylamine, 4-(N,N-diethylamino)benzylamine, 4-(N,N-diisopropylamino)benzylamine, N'-ethyl-N,N-dibenzylaminopropylamine, N,N-bisaminopropylbenzylamine, etc. can be mentioned.

[0100] As the second nitrogen-containing heterocyclic amine compound, any compound having a nitrogen-containing heterocyclic ring may be used. For example, N-(2-aminoethyl)pyrrolidine, N-(2-aminoethyl)piperidine, N-(2-aminoethyl)morpholine, N-(2-aminoethyl)piperazine, N-(2-aminoethyl)-N'-methylpiperazine, N-(3-aminopropyl)pyrrolidine, N-(3-aminopropyl)piperidine, N-(3-aminopropyl)morpholine, N-(3-aminopropyl)piperazine, N-(3-aminopropyl)-N'-methylpiperidine, etc. can be mentioned.

[0101] (3) Tertiary amine compound As the tertiary amine compound, it is a derivative of the above-mentioned secondary amine compound. For example, compounds obtained by reacting an amino group in the above-mentioned secondary amine compound with a carboxylic acid, an epoxy compound, an isocyanate compound, urea, etc. can be mentioned. More specifically, compounds obtained by reacting a primary amino group or a secondary amino group in the above-mentioned tertiary amine compound with a carboxylic acid, an epoxy compound, an isocyanate compound, urea, etc. can be mentioned. Regarding the above reaction, it can be the same as the content described for use in the modified imidazole compound. In the present disclosure, it is preferable that the above-mentioned tertiary amine compound contains a reaction product of a secondary amine compound and an epoxy compound. This is because the composition becomes excellent in low-temperature curability and storage stability. Regarding the epoxy compounds used for forming the above-mentioned tertiary amine compound and the epoxy compounds that can preferably be used, the same compounds as those listed as the compounds used for forming the above-mentioned modified imidazole are used.

[0102] The secondary amine compound constituting the above-mentioned tertiary amine compound preferably includes a compound having a primary amino group. This is because the synthesis of the above-mentioned tertiary amine compound is easy.

[0103] The number of tertiary amino groups in the secondary amine compound constituting the above-mentioned tertiary amine compound is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and particularly preferably 1. This is because the composition will be more excellent in low-temperature curability and storage stability.

[0104] The number of dihydrocarbon amino groups in the secondary amine compound constituting the above-mentioned tertiary amine compound as a tertiary amino group is preferably 1 or more, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, still more preferably 1 or more and 2 or less, and particularly preferably 1. This is because the composition will be more excellent in low-temperature curability and storage stability.

[0105] The secondary amine compound constituting the above-mentioned tertiary amine compound preferably contains a secondary aliphatic amine compound, more preferably contains a chain aliphatic amine compound, and further preferably contains N,N-dimethylaminoethylamine, N,N-diethylaminoethylamine, N,N-diisopropylaminoethylamine, N,N-diallylaminoethylamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-diisopropylaminopropylamine, N,N-diallylaminopropylamine, etc., and particularly preferably contains N,N-dimethylaminoethylamine, N,N-diethylaminoethylamine, N,N-diisopropylaminoethylamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-diisopropylaminopropylamine, etc. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0106] (4) Others The total content of the above-mentioned primary amine compound, the above-mentioned secondary amine compound, and the secondary amine compound constituting the above-mentioned tertiary amine compound is preferably 10 parts by mass or more and 45 parts by mass or less, more preferably 15 parts by mass or more and 40 parts by mass or less, still more preferably 20 parts by mass or more and 35 parts by mass or less, and particularly preferably 25 parts by mass or more and 35 parts by mass or less in 100 parts by mass in total of the above-mentioned imidazole-based compound and the above-mentioned tertiary amine compound. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0107] The total content of the above-mentioned primary amine compound, the above-mentioned secondary amine compound, and the secondary amine compound constituting the above-mentioned tertiary amine compound is preferably 5 parts by mass or more and 20 parts by mass or less, more preferably 10 parts by mass or more and 20 parts by mass or less, and still more preferably 12 parts by mass or more and 18 parts by mass or less in 100 parts by mass of the above composition. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0108] The total content of the above second amine compound constituting the above first amine compound, the above second amine compound, and the above third amine compound is preferably 5 parts by mass or more and 20 parts by mass or less, more preferably 10 parts by mass or more and 20 parts by mass or less, and still more preferably 12 parts by mass or more and 18 parts by mass or less in 100 parts by mass of the total amount of the above imidazole-based compound, the above tertiary amine compound, and the following phenolic resin. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0109] The content of the above tertiary amine compound is preferably 1 part by mass or more and 60 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, still more preferably 10 parts by mass or more and 45 parts by mass or less, particularly preferably 15 parts by mass or more and 40 parts by mass or less, still more preferably 20 parts by mass or more and 35 parts by mass or less, and particularly preferably 25 parts by mass or more and 35 parts by mass or less in 100 parts by mass of the above composition. This is because the above composition becomes excellent in low-temperature curability and storage stability.

[0110] 3. Phenolic resin The composition of the present disclosure preferably contains a phenolic resin as a component other than the imidazole-based compound and the tertiary amine compound. This is because the above composition can be used as a curing agent excellent in the balance between storage stability and low-temperature curability.

[0111] The above phenolic resin is a compound having two or more phenolic hydroxyl groups (excluding bisphenol A). Examples of such phenolic resins include phenol novolak resins (polyhydric phenol compounds in which phenol nuclei are linked by methylene groups), cresol novolak resins (polyhydric phenol compounds in which cresol nuclei are linked by methylene groups), aromatic hydrocarbon formaldehyde resin-modified phenolic resins, dicyclopentadiene phenol addition type resins (polyhydric phenol compounds in which phenol nuclei are linked by dicyclopentadiene groups), phenol aralkyl resins (polyhydric phenol compounds in which phenol nuclei are linked by divalent groups containing aromatic rings such as phenylene groups and biphenylene groups, Zylock resins), naphthol aralkyl resins, trisphenolmethane resins, tetraphenolethane resins, naphthol novolak resins, naphthol-phenol co-condensed novolak resins, naphthol-cresol co-condensed novolak resins, biphenyl-modified phenolic resins (polyhydric phenol compounds in which phenol nuclei are linked by bismethylene groups), biphenyl-modified naphthol resins (polyhydric naphthol compounds in which phenol nuclei are linked by bismethylene groups), aminotriazine-modified phenolic resins (compounds having a phenol skeleton, a triazine ring and a primary amino group in the molecular structure), and alkoxy group-containing aromatic ring-modified novolak resins (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked by formaldehyde), and other polyhydric phenol compounds.

[0112] Examples of phenolic resins include Phenol Novolak H-1, H-2, H-3, H-4, H-5, MEP-1100-N manufactured by Meiwafosis Co., Ltd., Phenol Novolak (PSM series, for example, PSM-4326) manufactured by Gunei Chemical Industry Co., Ltd., Ortho Cresol Novolak MER-130, Trisphenolmethane type MEH-7500, Tetrakisphenol type MEH-7600, Naphthol type MEH-7700, Phenol Aralkyl type MEH-7800, MEH-7851, Trisphenol type R-3, Bisphenol Novolak type MEP-6309, MEP-6309E, Liquid Phenol Novolak MEH-8000H, MEH-8005, MEH-8010, MEH-8015, MEH-8205, and the like. Examples of dicyclopentadiene phenol epoxy resins include, for example, Examples include ERM-6085, ERM-6095, ERM-6105, ERM-6115, ERM-6125, or ERM-6140 manufactured by SONGWON.

[0113] In the present disclosure, the linking group that links phenols constituting the phenol resin is preferably an alkylene group such as a methylene group or an alicyclic group such as a dicyclopentadiene group, more preferably including a phenol novolak resin, a cresol novolak resin, and a dicyclopentadiene phenol addition type resin, and still more preferably including a phenol novolak resin and a dicyclopentadiene phenol addition type resin. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0114] In the present disclosure, the hydroxyl equivalent of the above phenol resin is preferably 70 g / eq or more and 300 g / eq or less, more preferably 80 g / eq or more and 280 g / eq or less, and still more preferably 100 g / eq or more and 250 g / eq or less. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0115] The content of the above phenol resin is preferably 20 parts by mass or more and 80 parts by mass or less, more preferably 30 parts by mass or more and 70 parts by mass or less, and particularly preferably 40 parts by mass or more and 60 parts by mass or less in 100 parts by mass of the above composition. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0116] The content of the above phenol resin is preferably 20 parts by mass or more and 500 parts by mass or less, more preferably 50 parts by mass or more and 300 parts by mass or less, still more preferably 60 parts by mass or more and 200 parts by mass or less, still more preferably 70 parts by mass or more and 150 parts by mass or less, and particularly preferably 80 parts by mass or more and 120 parts by mass or less, based on 100 parts by mass in total of the above imidazole compound and the tertiary amine compound. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0117] 4. Bisphenol A The above composition may contain bisphenol A (4,4'-isopropylidene bisphenol). This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0118] The content of bisphenol A is preferably 1 mass ppm or more and 25,000 mass ppm or less, preferably 2 mass ppm or more and 15,000 mass ppm or less, more preferably 3 mass ppm or more and 2,000 mass ppm or less, still more preferably 5 mass ppm or more and 1,000 mass ppm or less, still more preferably 10 mass ppm or more and 500 mass ppm or less, still more preferably 20 mass ppm or more and 300 mass ppm or less, still more preferably 30 mass ppm or more and 200 mass ppm or less, and particularly preferably 40 mass ppm or more and 100 mass ppm or less, based on the total content of the above imidazole compound and the tertiary amine compound. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0119] The content of the above bisphenol A is preferably 1 mass ppm or more and 15,000 mass ppm or less, more preferably 2 mass ppm or more and 10,000 mass ppm or less, still more preferably 3 mass ppm or more and 1,000 mass ppm or less, even more preferably 5 mass ppm or more and 500 mass ppm or less, further more preferably 10 mass ppm or more and 200 mass ppm or less, still further more preferably 15 mass ppm or more and 100 mass ppm or less, and particularly preferably 20 mass ppm or more and 40 mass ppm or less in the above composition. This is because the above composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0120] Examples of the method for measuring the content of the above bisphenol A include a method of measuring by an internal standard method using a liquid chromatograph mass spectrometer (LC-MS / MS). More specifically, the above measurement method is to prepare a calibration curve by measuring a solution in which bisphenol A and bisphenol A-d as an internal standard are dissolved while changing the concentration of bisphenol A. Then, the composition to be measured is dissolved in a solvent such as DMF, and bisphenol A-d 16 is added as an internal standard, and after dilution, it is measured under the same conditions, and the concentration of bisphenol A in the composition can be measured using the calibration curve. 16 For the measuring device, measuring conditions, etc. used in the above measurement, the following contents can be adopted.

[0121] <Measuring device> LC: ACQUITY PREMIER (Waters) MS: Xevo TQ-XS (Waters) Column: L-kolumn ODS-3 (2.1 * 150 mm, 3 μm) <Measuring conditions> Solvent A: Acetonitrile Solvent B: 0.01% Aqueous ammonium acetate solution Column Temp.: 40 °C Flow: 0.4 mL / min A(%) : 40(0 min) - 40(5 min) - 95(8 min) - 95(13 min) - 40(13.1 min) - 23(23 min) Injection volume: 1 μL <Mass Method> Ionization mode: ESI Negative capillary: 2 kV Cone Source temp.: 150 °C Desolvation temp.: 500 °C Cone gas flow: 150 L / h Desolvation gas flow: 1000 L / h Collision gas flow: 0.15 mL / min Nebliser gas flow: 7 bar Measurement mode: MRM BPA Cone: 25 V Collision: 29 eV Transition: 227.0 / 133.0, 210.9 BPA - d16 Cone: 22 V Collision: 32 eV Transition: 241.0 / 142.0

[0122] Regarding the method for adjusting the content of bisphenol A above, examples include the amount of bisphenol A generated during the preparation of imidazole-based compounds and tertiary amine compounds, and methods for adjusting the compounding amounts added to imidazole-based compounds and tertiary amine compounds.

[0123] 5. Others The above composition may contain components other than imidazole-based compounds, tertiary amine compounds, phenolic resins, and bisphenol A.

[0124] Examples of the above composition include curing agent compositions such as anionic curing agents used for curing epoxy compounds and the like. Among them, it is preferably used for combination with a thiol compound. This is because the effects of the present disclosure can be more effectively exhibited.

[0125] As a method of using the above curing agent composition, any method can be used as long as it can exhibit the desired curability. It may be a method of using it as a thermosetting agent that exhibits curability by heating, or a method of using it as a photocuring agent that exhibits curability by energy ray irradiation. In the present disclosure, it is preferable that the above composition is used as a thermosetting agent. This is because the effect of excellent storage stability can be more effectively exhibited.

[0126] Examples of the curable composition containing the above composition as a curing agent composition include adhesives, paints, fiber-reinforced composite materials, and the like. Examples of the above adhesive include semiconductor encapsulants, electronic component encapsulants, laminating agents for printed wiring boards, electronic component adhesives, structural adhesives, and the like.

[0127] B. Composition Next, the composition of the present disclosure (hereinafter, may be referred to as composition B) will be described. The composition B of the present disclosure is a composition containing an imidazole-based compound, a tertiary amine compound other than the above imidazole-based compound, and a thiol compound, wherein the tertiary amine compound is a first amine compound having only a tertiary amino group as an amino group, a second amine compound having a tertiary amino group and at least one of a primary amino group or a secondary amino group, and a third amine compound which is a derivative of the second amine compound, and the total content of the second amine compound constituting the first amine compound, the second amine compound, and the third amine compound is 10 parts by mass or more and 45 parts by mass or less in 100 parts by mass in total of the imidazole-based compound and the tertiary amine compound.

[0128] According to the present disclosure, by having the imidazole compound, the tertiary amine compound, and the thiol compound, it can be used as a curing agent excellent in storage stability and low-temperature curability.

[0129] The composition B of the present disclosure contains an imidazole compound, a tertiary amine compound, and a thiol compound. Hereinafter, each component of the composition B of the present disclosure will be described in detail.

[0130] 1. Imidazole compound The content of the imidazole compound is preferably 0.01 part by mass or more and 10 parts by mass or less, more preferably 0.1 part by mass or more and 5 parts by mass or less, still more preferably 0.5 part by mass or more and 3 parts by mass or less, and particularly preferably 1 part by mass or more and 2 parts by mass or less in 100 parts by mass of the composition B. This is because the composition B can be used as a curing agent excellent in the balance between storage stability and low-temperature curability.

[0131] The total content of the imidazole compound and the tertiary amine compound is preferably 0.1 part by mass or more and 10 parts by mass or less, more preferably 0.5 part by mass or more and 5 parts by mass or less, still more preferably 1 part by mass or more and 3 parts by mass or less in 100 parts by mass of the composition B. This is because the composition B can be used as a curing agent excellent in the balance between storage stability and low-temperature curability.

[0132] Regarding other details of the imidazole compound, since they are the same as the description in the above "A. Composition", the description here is omitted.

[0133] 2. Tertiary amine compound It is preferable that the content of the above tertiary amine compound is 0.01 part by mass or more and 10 parts by mass or less, more preferably 0.05 part by mass or more and 5 parts by mass or less, still more preferably 0.1 part by mass or more and 3 parts by mass or less, and particularly preferably 0.2 part by mass or more and 1 part by mass or less, in 100 parts by mass of the above composition B. This is because the above composition B can be used as a curing agent having an excellent balance between storage stability and low-temperature curability.

[0134] Regarding other details of the above tertiary amine compound, since they are the same as the description given in the above "A. Composition", the description here is omitted.

[0135] 3. Thiol compound The above thiol compound is included as a component other than the above imidazole-based compound and tertiary amine compound. As the above thiol compound, those generally used as anionic curing agents such as curing agents for epoxy compounds can be used.

[0136] The number of thiol groups in the above thiol compound may be 1 or more, preferably 2 or more and 10 or less, more preferably 3 or more and 8 or less, and still more preferably 3 or more and 6 or less. This is because the effects of the present disclosure can be more efficiently exhibited.

[0137] The molecular weight of the above thiol compound is not particularly limited as long as the desired effects can be obtained, but it is preferably 100 or more and 800 or less, more preferably 200 or more and 600 or less, and particularly preferably 300 or more and 500 or less. This is because the effects of the present disclosure can be more efficiently exhibited.

[0138] Examples of such thiol compounds include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), dipentaerythritol hexakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptobutyrate), 1,3,4,6-tetrakis(2-mercaptoethyl)-1,3,4,6-tetraazaoctahydropentalene-2,5-dione, 1,3,5-tris(3-mercaptopropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-, 4,7- or 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluril, and the like. Examples of commercially available thiol compounds include TS-G manufactured by Shikoku Chemicals Corporation, TEMP, DPMP, PEMP manufactured by SC Organic Chemicals Co., Ltd., and PETG manufactured by Yodo Chemical Co., Ltd.

[0139] In the present disclosure, it is preferable that the thiol compound is a polythiol having a heterocyclic ring containing at least one nitrogen in the ring, such as 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluril and 1,3,5-tris(3-mercaptopropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and more preferably a compound having a glycoluril structure. This is because the effects of the present disclosure can be more efficiently exhibited.

[0140] The content of the thiol compound is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 90 parts by mass or more and 99 parts by mass or less in 100 parts by mass of the composition B. This is because the effects of the present disclosure can be more efficiently exhibited.

[0141] The content of the thiol compound is preferably 1,000 parts by mass or more and 20,000 parts by mass or less, more preferably 3,000 parts by mass or more and 15,000 parts by mass or less, and still more preferably 5,000 parts by mass or more and 10,000 parts by mass or less, based on 100 parts by mass of the imidazole-based compound. This is because the effects of the present disclosure can be more efficiently exhibited.

[0142] The content of the thiol compound is preferably 2,000 parts by mass or more and 40,000 parts by mass or less, more preferably 6,000 parts by mass or more and 30,000 parts by mass or less, and still more preferably 10,000 parts by mass or more and 20,000 parts by mass or less, based on 100 parts by mass of the tertiary amine compound. This is because the effects of the present disclosure can be more efficiently exhibited.

[0143] The content of the thiol compound is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, still more preferably 90 parts by mass or more and 99 parts by mass or less, and particularly preferably 92 parts by mass or more and 98 parts by mass or less, in 100 parts by mass in total of the imidazole-based compound, the tertiary amine compound and the thiol compound. This is because the effects of the present disclosure can be more efficiently exhibited.

[0144] The total content of the imidazole-based compound, the tertiary amine compound and the thiol compound is preferably 60 parts by mass or more, more preferably 80 parts by mass or more, still more preferably 90 parts by mass or more, and particularly preferably 95 parts by mass or more, in 100 parts by mass of the composition B. This is because the effects of the present invention can be efficiently exhibited.

[0145] 4. Phenolic resin The composition B preferably contains a phenolic resin. This is because the effects of the present disclosure can be efficiently exhibited. Regarding the content of such a phenolic resin, since it is the same as the description in the section of "A. Composition" above, the description here is omitted.

[0146] As the content of the above phenol resin, it is preferably 0.1 part by mass or more and 10 parts by mass or less, more preferably 0.5 part by mass or more and 5 parts by mass or less, and still more preferably 1 part by mass or more and 3 parts by mass or less in 100 parts by mass of the above composition B. This is because the effects of the present disclosure can be more effectively exhibited.

[0147] As the total content of the above phenol resin, imidazole-based compound and tertiary amine compound, it is preferably 0.1 part by mass or more and 15 parts by mass or less, preferably 0.5 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less, and particularly preferably 2 parts by mass or more and 5 parts by mass or less in 100 parts by mass of the above composition B. This is because the effects of the present disclosure can be more efficiently exhibited.

[0148] 5. Bisphenol A The curable composition of the present disclosure may contain bisphenol A. This is because the effects of the present disclosure can be efficiently exhibited. Regarding the content of such bisphenol A, since it is the same as the description in the section of "A. Composition" above, the description here is omitted.

[0149] 6. Others The above composition B can contain other components other than the imidazole-based compound, tertiary amine compound, phenol resin and bisphenol A.

[0150] Regarding the use of the above composition B, since it is the same as the description in the section of "A. Composition" above, the description here is omitted.

[0151] C. Curable Composition Next, the curable composition of the present disclosure will be described. The curable composition of the present disclosure is a curable composition containing an imidazole-based compound, a tertiary amine compound other than the above imidazole-based compound, and a curable compound, wherein the tertiary amine compound is a first amine compound having only a tertiary amino group as an amino group, a second amine compound having a tertiary amino group and at least one of a primary amino group or a secondary amino group, and a third amine compound which is a derivative of the second amine compound, and contains at least one selected from the group consisting of the first amine compound, the second amine compound, and the third amine compound, and the total content of the second amine compound constituting the first amine compound, the second amine compound, and the third amine compound is 10 parts by mass or more and 45 parts by mass or less in 100 parts by mass in total of the imidazole-based compound and the tertiary amine compound.

[0152] According to the present disclosure, by having an imidazole-based compound and a predetermined amount of a tertiary amine compound, it has excellent low-temperature curability and storage stability.

[0153] The curable composition of the present disclosure contains an imidazole-based compound, a tertiary amine compound, and a curable compound. Hereinafter, each component of the curable composition of the present disclosure will be described in detail.

[0154] 1. Imidazole-based compound The content of the imidazole-based compound is preferably 0.01 part by mass or more and 10 parts by mass or less, more preferably 0.1 part by mass or more and 5 parts by mass or less, still more preferably 0.2 part by mass or more and 3 parts by mass or less, and particularly preferably 0.3 part by mass or more and 1 part by mass or less in 100 parts by mass of the curable composition. This is because the effects of the present disclosure can be more efficiently exhibited.

[0155] The content of the above imidazole compound is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, still more preferably 0.2 to 5 parts by mass, and particularly preferably 0.3 to 3 parts by mass with respect to 100 parts by mass of the above curable compound. This is because the effects of the present disclosure can be more efficiently exhibited.

[0156] The total content of the above imidazole compound and tertiary amine compound is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, still more preferably 0.2 to 5 parts by mass, further preferably 0.3 to 3 parts by mass, and particularly preferably 0.5 to 1.5 parts by mass in 100 parts by mass of the above curable composition. This is because the effects of the present disclosure can be more efficiently exhibited.

[0157] The total content of the above imidazole compound and tertiary amine compound is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, still more preferably 0.3 to 5 parts by mass, further preferably 0.4 to 3 parts by mass, and particularly preferably 0.5 to 1.5 parts by mass with respect to 100 parts by mass of the above curable compound. This is because the effects of the present disclosure can be more efficiently exhibited.

[0158] Since the above imidazole compound is the same as the description in the section of "A. Composition" above, the description here is omitted.

[0159] 2. Tertiary Amine Compound The content of the above tertiary amine compound is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 3 parts by mass, and still more preferably 0.1 to 1 part by mass in 100 parts by mass of the above curable composition. This is because the effects of the present disclosure can be more efficiently exhibited.

[0160] The content of the above tertiary amine compound is preferably 0.01 part by mass or more and 10 parts by mass or less, more preferably 0.1 part by mass or more and 5 parts by mass or less, still more preferably 0.2 part by mass or more and 3 parts by mass or less, and particularly preferably 0.3 part by mass or more and 1 part by mass or less, based on 100 parts by mass of the above curable compound. This is because the effects of the present disclosure can be more effectively exerted. Regarding the above tertiary amine compound, since it is the same as the description in the section of "A. Composition" above, the description here is omitted.

[0161] 3. Curable compound The above curable compound may be any compound that can be polymerized by the above imidazole-based compound and tertiary amine compound. Examples of such curable compounds include cyclic compounds, chain conjugated diene monomers, vinyl aromatic monomers, polar vinyl monomers, α-olefin monomers (ethylene, propylene, etc.). In the present disclosure, it is preferable that the above curable compound contains a cyclic compound. This is because the effects of the present disclosure can be more efficiently exerted.

[0162] Examples of the above cyclic compounds include epoxy compounds, cyclic lactones, cyclic lactams, cyclic siloxanes, etc. In the present disclosure, it is preferable that the above cyclic compound contains an epoxy compound. This is because the effects of the present disclosure can be more efficiently exerted.

[0163] The above epoxy compound can be the same as the compounds described in the section of "A. Composition" above.

[0164] Examples of the above cyclic lactones, cyclic lactams, cyclic siloxanes, etc. include the compounds described in International Publication No. 2022 / 138769. Examples of the above chain conjugated diene monomers, vinyl aromatic monomers, polar vinyl monomers, etc. include the compounds described in Japanese Patent No. 6184676.

[0165] As the content of the above-mentioned curable compound, it is preferably 10 parts by mass or more and 99 parts by mass or less, more preferably 30 parts by mass or more and 90 parts by mass or less, still more preferably 50 parts by mass or more and 80 parts by mass or less, and particularly preferably 60 parts by mass or more and 70 parts by mass or less in 100 parts by mass of the above-mentioned curable composition. This is because the effects of the present disclosure can be more efficiently exerted.

[0166] 4. Thiol compound The curable composition of the present disclosure preferably contains a thiol compound. This is because the effects of the present disclosure can be effectively exerted. Regarding the content of such a thiol compound, since it is the same as the description in the section of "B. Composition" above, the description here is omitted.

[0167] As the content of the above-mentioned thiol compound, it is preferably 5 parts by mass or more and 70 parts by mass or less, more preferably 10 parts by mass or more and 60 parts by mass or less, still more preferably 20 parts by mass or more and 50 parts by mass or less, and particularly preferably 25 parts by mass or more and 40 parts by mass or less in 100 parts by mass of the above-mentioned curable composition. This is because the effects of the present disclosure can be more efficiently exerted.

[0168] As the content of the above-mentioned thiol compound, it is preferably 5 parts by mass or more and 70 parts by mass or less, more preferably 10 parts by mass or more and 60 parts by mass or less, still more preferably 20 parts by mass or more and 50 parts by mass or less, and particularly preferably 25 parts by mass or more and 40 parts by mass or less in 100 parts by mass of the total of the above-mentioned imidazole-based compound, tertiary amine compound, curable compound and thiol compound. This is because the effects of the present disclosure can be more efficiently and effectively exerted.

[0169] The content of the thiol compound is preferably 10 parts by mass or more and 100 parts by mass or less, more preferably 20 parts by mass or more and 80 parts by mass or less, still more preferably 30 parts by mass or more and 70 parts by mass or less, and particularly preferably 40 parts by mass or more and 60 parts by mass or less, based on 100 parts by mass of the curable compound. This is because the effects of the present disclosure can be more efficiently exhibited.

[0170] 5. Phenolic resin The curable composition of the present disclosure preferably contains a phenolic resin. This is because the effects of the present disclosure can be effectively exhibited. Regarding the content of such a phenolic resin, since it is the same as the description in the section of "A. Composition" above, the description here is omitted.

[0171] The content of the phenolic resin is preferably 0.01 part by mass or more and 10 parts by mass or less, more preferably 0.1 part by mass or more and 5 parts by mass or less, still more preferably 0.2 part by mass or more and 3 parts by mass or less, and particularly preferably 0.3 part by mass or more and 1 part by mass or less, per 100 parts by mass of the curable composition. This is because the effects of the present disclosure can be more efficiently exhibited.

[0172] The total content of the phenolic resin, imidazole-based compound, and tertiary amine compound is preferably 0.01 part by mass or more and 10 parts by mass or less, more preferably 0.5 part by mass or more and 5 parts by mass or less, still more preferably 1 part by mass or more and 3 parts by mass or less, per 100 parts by mass of the curable composition. This is because the effects of the present disclosure can be more efficiently exhibited.

[0173] 6. Bisphenol A The curable composition of the present disclosure may contain bisphenol A. This is because the effects of the present disclosure can be efficiently exhibited. Regarding the content of such bisphenol A, since it is the same as the description in the section of "A. Composition" above, the description here is omitted.

[0174] 7. Others The composition of the present disclosure may be a composition having the above imidazole-based compound, tertiary amine compound, curable compound, thiol compound, phenolic resin, and other components other than bisphenol A. Examples of such other components include blocked isocyanate, filler, isocyanate curing catalyst, plasticizer, colorant, antioxidant, foaming agent, diluent, ultraviolet absorber, and the like.

[0175] Regarding the embodiments of the curable composition of the present disclosure, the same content as described in the section of "A. Composition" above can be adopted.

[0176] D. Cured Product Next, the cured product of the present disclosure will be described. The cured product of the present disclosure is the cured product of the above-described curable composition. According to the present disclosure, by using the above-described curable composition, the formation of a cured product is easy, and the quality stability is excellent.

[0177] Regarding the content of the above curable composition, since it is the same as the description in the section of "C. Curable Composition" above, the description here is omitted. Regarding the manufacturing method of the above cured product, any method can be used as long as it can form a cured product in a desired cured state. For example, the method described in the section of "E. Manufacturing Method of Cured Product" described later can be used. As the use of the cured product of the present disclosure, for example, the same content as described in the section of "A. Composition" above can be adopted.

[0178] E. Manufacturing Method of Cured Product Next, the manufacturing method of the cured product of the present disclosure will be described. The manufacturing method of the cured product of the present disclosure is characterized by including a step of heating the above-described curable composition. According to the present disclosure, by using the above-described curable composition, the formation of a cured product is easy, and the manufacturing of a cured product with excellent quality stability becomes easy.

[0179] The manufacturing method of the cured product of the present disclosure includes a step of heating. Hereinafter, each step of the method for producing the cured product of the present disclosure will be described.

[0180] 1. Heating step This step is a step of heating the above-described curable composition. Since the content of the above curable composition is the same as the description in the section of "C. Curable composition" above, the description here is omitted.

[0181] The heating temperature of the above curable composition may be any temperature capable of forming a desired cured product. For example, it can be 60°C or higher and 150°C or lower. In the present disclosure, when the above curable composition contains a thiol compound, the heating temperature is preferably 70°C or higher and 110°C or lower, more preferably 75°C or higher and 100°C or lower, and even more preferably 80°C or higher and 90°C or lower. This is because the effects of the present disclosure can be more efficiently exhibited.

[0182] 2. Others The production method of the present disclosure includes the above heating step, and may include other steps as necessary. Examples of the above other steps include a coating step of coating the above composition. As an embodiment of the cured product produced by the production method of the present disclosure, for example, it can be the same as the content described in the section of "A. Composition" above.

[0183] F. Others In the present disclosure, the following aspects are included. [1] A composition containing an imidazole-based compound and a tertiary amine compound other than the above imidazole-based compound, wherein the tertiary amine compound is at least one selected from a first amine compound having only a tertiary amino group as an amino group, a second amine compound having a tertiary amino group and at least one of a primary amino group or a secondary amino group, and a third amine compound which is a derivative of the second amine compound, and the total content of the second amine compound constituting the first amine compound, the second amine compound, and the third amine compound is 10 parts by mass or more and 45 parts by mass or less in 100 parts by mass in total of the imidazole-based compound and the tertiary amine compound. [2] The composition according to [1], wherein the total content of the second amine compound constituting the first amine compound, the second amine compound, and the third amine compound is 5 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition. [3] The composition according to [1] or [2], wherein the imidazole-based compound contains a modified imidazole compound. [4] The composition according to any one of [1] to [3], wherein the tertiary amino group contains a dihydrocarbon amino group. [5] The composition according to any one of [1] to [4], wherein the number of the dihydrocarbon amino groups is 1 or more and 5 or less in the tertiary amine compound. [6] The composition according to any one of [1] to [5], wherein the second amine compound constituting the first amine compound, the second amine compound, and the third amine compound contains an aliphatic compound. [7] The composition according to any one of [1] to [6], wherein the third amine compound is a reaction product of the second amine compound and an epoxy compound. [8] The composition according to any one of [1] to [7], wherein the composition contains a phenolic resin. [9] The composition according to any one of [1] to [8], wherein the composition contains bisphenol A.

[10] The composition according to [9], wherein the content of the bisphenol A is 1 ppm or more and 30,000 ppm or less with respect to the total of the imidazole-based compound and the tertiary amine compound.

[11] A composition containing an imidazole-based compound, a tertiary amine compound other than the imidazole-based compound, and a thiol compound, wherein the tertiary amine compound contains at least one selected from a first amine compound having only a tertiary amino group as an amino group, a second amine compound having a tertiary amino group and at least one of a primary amino group and a secondary amino group, and a third amine compound which is a derivative of the second amine compound, and the total content of the second amine compound constituting the first amine compound, the second amine compound, and the third amine compound is 10 parts by mass or more and 45 parts by mass or less in 100 parts by mass in total of the imidazole-based compound and the tertiary amine compound.

[12] A curable composition containing an imidazole-based compound, a tertiary amine compound other than the imidazole-based compound, and a curable compound, wherein the tertiary amine compound contains at least one selected from a first amine compound having only a tertiary amino group as an amino group, a second amine compound having a tertiary amino group and at least one of a primary amino group and a secondary amino group, and a third amine compound which is a derivative of the second amine compound, and the total content of the second amine compound constituting the first amine compound, the second amine compound, and the third amine compound is 10 parts by mass or more and 45 parts by mass or less in 100 parts by mass in total of the imidazole-based compound and the tertiary amine compound.

[13] The curable composition according to

[12] , wherein the curable composition contains a thiol compound.

[14] A cured product of the curable composition according to

[12] .

[15] A method for producing a cured product, comprising a heating step of heating the curable composition described in

[12] .

[0184] The present disclosure is not limited to the above embodiments. The above embodiments are examples, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits the same effects is included in the technical scope of the present disclosure.

Examples

[0185] Hereinafter, the present disclosure will be described in more detail with reference to Examples and Comparative Examples, but the present disclosure is not limited to these Examples and the like.

[0186] 19.6 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Co., Ltd.) and 16.3 g of toluene were added to a flask, and the temperature was raised with stirring until the internal temperature reached 70°C. 26.0 g of EP-4100E (bisphenol A diglycidyl ether, manufactured by ADEKA Corporation, EEW: 190 g / eq) previously heated to 70°C was added to this 2E4MZ toluene solution so that the internal temperature was between 65 and 75°C. The addition amount of 2E4MZ is an amount that becomes 1.3 mol with respect to 1.0 mol of the epoxy groups of the epoxy compound EP-4100E. After the addition of EP-4100E was completed, the internal temperature was raised to 100°C and heated for 1 hour to obtain a mixture of a reaction product of 2E4MZ and EP-4100E (modified imidazole compound) as an imidazole-based compound and unreacted 2E4MZ (imidazole compound; 0.3 mol with respect to 1.0 mol of the epoxy groups of EP-4100E). After completion of heating, the internal temperature was raised to 140°C, toluene was distilled off under normal pressure, and then the system was depressurized to distill off toluene at less than 5 kPa. The pressure was released, and while raising the internal temperature to 180 °C, 51.0 g of MEP-1100-N (phenol novolak resin, manufactured by Meiwa Kasei Co., Ltd.) was added. Thereafter, the inside of the system was depressurized, degassed at 180 °C and less than 5 kPa, the pressure was then released, and 5.1 g of tetramethylethylenediamine (TMEDA, a primary amine compound) was added dropwise. After the dropping was completed, it was refluxed until the boiling of TMEDA ceased to obtain Composition 1.

[0187] Composition 2 was obtained in the same manner as in Example 1, except that 16.6 g of 2E4MZ, 13.8 g of toluene, 22.0 g of EP-4100E, 49.0 g of MEP-1100-N, and 9.7 g of TMEDA were used.

[0188] Composition 3 was obtained in the same manner as in Example 1, except that 13.9 g of 2E4MZ, 11.6 g of toluene, 18.4 g of EP-4100E, 47.0 g of MEP-1100-N, and 13.8 g of TMEDA were used.

[0189] Composition 4 was obtained in the same manner as in Example 1, except that 14.0 g of 2E4MZ, 11.7 g of toluene, 18.7 g of EP-4100E, 47.0 g of MEP-1100-N, and 14.0 g of N,N-dimethylaminopyridine (DMAP, a primary amine compound) were used.

[0190] 2E4MZ (4.6 g) and toluene (3.9 g) were added to the flask, and the temperature was raised with stirring until the internal temperature reached 70 °C. To this 2E4MZ toluene solution, EP-4100E (6.2 g) preheated to 70 °C was added so that the internal temperature was between 65 and 75 °C. The added amount of 2E4MZ is an amount such that it is 1.3 mol with respect to 1.0 mol of the epoxy groups of the epoxy compound EP-4100E. After the addition of EP-4100E was completed, the internal temperature was raised to 100 °C and heated for 1 hour to obtain a mixture of a reaction product of 2E4MZ and EP-4100E (modified imidazole compound) as an imidazole-based compound and unreacted 2E4MZ (imidazole compound; 0.3 mol per 1.0 mol of the epoxy groups of EP-4100E). 15.8 g of N,N-dimethylaminopropylamine (DMAPA, manufactured by BASF, a secondary amine compound) and 14.0 g of toluene were added to another flask, and the temperature was raised with stirring until the internal temperature reached 70°C. EP-4100E (29.4 g) previously heated to 70°C was added to this DMAPA / toluene solution so that the internal temperature was between 65 and 75°C. The addition amount of DMAPA is an amount that becomes 1.0 mol with respect to 1.0 mol of epoxy groups of the epoxy compound EP-4100E. After the addition of EP-4100E was completed, the internal temperature was raised to 100°C and heated for 1 hour to obtain a reaction product of DMAPA and EP-4100E (a tertiary amine compound) as a tertiary amine compound. After completion of heating, it was combined with the previous solution, the internal temperature was raised to 140°C, toluene was distilled off under normal pressure, and then the system was depressurized to distill off toluene at less than 5 kPa. The pressure was released, and MEP-1100-N (57.0 g) was added while raising the internal temperature to 180°C. Then, the system was depressurized and degassed at 180°C and less than 5 kPa to obtain Composition 5.

[0191] Composition 6 was obtained in the same manner as in Example 1, except that 14.0 g of 2E4MZ, 11.7 g of toluene, 18.4 g of EP-4100E, 47.0 g of MEP-1100-N were used, and 13.0 g of tetramethylethylenediamine (PMDETA, a primary amine compound) was added instead of TMEDA.

[0192] Composition 7 was obtained in the same manner as in Example 1, except that 13.9 g of 2E4MZ, 11.6 g of toluene, 18.4 g of EP-4100E, 50.0 g of MEP-1100-N, and 18.0 g of TMEDA were used.

[0193] Bisphenol A was added to Composition 3 obtained in Example 3 so as to be 1% by mass to obtain Composition 8.

[0194] Composition 9 was obtained in the same manner as in Example 1, except that 10.5 g of 2-methylimidazole (2MZ, manufactured by Shikoku Kasei Co., Ltd.) was used instead of 2E4MZ, 11.6 g of toluene, 18.4 g of EP-4100E, 43.0 g of MEP-1100-N, and 13.0 g of TMEDA were used.

[0195] Composition 10 was obtained in the same manner as in Example 1, except that 10.8 g of 2E4MZ, 11.6 g of toluene, 18.4 g of EP-4100E, 45.0 g of MEP-1100-N, and 13.8 g of TMEDA were used. Since the addition amount of 2E4MZ is an amount that becomes 1.0 mol with respect to 1.0 mol of the epoxy groups of the epoxy compound EP-4100E, the imidazole-based compound obtained in this example does not contain free 2E4MZ (imidazole compound).

[0196] Composition 11 was obtained in the same manner as in Example 1, except that 20.0 g of 2E4MZ, 11.6 g of toluene, 18.4 g of EP-4100E, 52.0 g of MEP-1100-N, and 15.0 g of TMEDA were used. Since the addition amount of 2E4MZ is an amount that becomes 1.9 mol with respect to 1.0 mol of the epoxy groups of the epoxy compound EP-4100E, the imidazole-based compound obtained in this example is a mixture of a reaction product of 2E4MZ and EP-4100E (modified imidazole compound) and unreacted 2E4MZ (imidazole compound; 0.9 mol portion with respect to 1.0 mol of the epoxy groups of EP-4100E).

[0197] Composition 12 was obtained in the same manner as in Example 1, except that 13.9 g of 2E4MZ, 11.6 g of toluene, 18.4 g of EP-4100E, 20.0 g of MEP-1100-N, and 13.8 g of TMEDA were used.

[0198] Composition 13 was obtained in the same manner as in Example 1, except that 13.9 g of 2E4MZ, 11.6 g of toluene, 18.4 g of EP-4100E, 110.0 g of MEP-1100-N, and 13.8 g of TMEDA were used.

[0199] Composition 14 was obtained in the same manner as in Example 1, except that 13.9 g of 2E4MZ, 11.6 g of toluene, 18.4 g of EP-4100E, 110.0 g of MEP-1100-N, and 13.8 g of 1,4-diazabicyclo[2.2.2]octane (DABCO, a primary amine compound) were used.

[0200] Comparative Composition 1 was obtained in the same manner as in Example 1, except that TMEDA was not added.

[0201] Comparative Composition 2 was obtained in the same manner as in Example 1, except that 9.1 g of 2E4MZ, 7.6 g of toluene, 12.1 g of EP-4100E, 44.0 g of MEP-1100-N, and 21.2 g of TMEDA were used.

[0202] Comparative Composition 3 was obtained in the same manner as in Example 5, except that 19.3 g of 2E4MZ, 16.1 g of toluene, 25.6 g of the first addition of EP-4100E, 3.2 g of DMAPA, 5.9 g of the second addition of EP-4100E, and 43.4 g of MEP-1100-N were used. Note that the addition amount of DMAPA is an amount that becomes 1.0 mol with respect to 1.0 mol of the epoxy groups of the epoxy compound EP-4100E. Therefore, in this comparative example, it contains the reaction product of DMAPA and EP-4100E (a tertiary amine compound) as the tertiary amine compound.

[0203] Bisphenol A was added to Comparative Composition 1 obtained in Comparative Example 1 so that the content became 1% by mass to obtain Comparative Composition 4.

[0204] Comparative Composition 5 was obtained in the same manner as in Example 1, except that 13.9 g of 2E4MZ, 16.1 g of toluene, 18.4 g of EP-4100E, 47.0 g of MEP-1100-N, and 3.0 g of TMEDA were used.

[0205] 13.8 g of TMEDA was added to pre-heated MEP-1100-N (13.8 g) at 180°C. After the dropping was completed, the mixture was refluxed until the boiling of TMEDA ceased to obtain Comparative Composition 6.

[0206] 1. Content of bisphenol A A solution prepared by dissolving bisphenol A and bisphenol A-d as an internal standard 16 was used to create a calibration curve by measuring it with different bisphenol A concentrations. Then, the composition to be measured was dissolved with a DMF solvent, and bisphenol A-d 16 was added as an internal standard solution. After dilution, it was measured under the same conditions, and the concentration of bisphenol A in the composition was measured using the calibration curve. The results are shown in Tables 1 to 2 below. Note that Example 8 and Comparative Example 3 were prepared such that the content of bisphenol A was 10,000 ppm. In addition, "BPA / composition" in Tables 1 to 3 represents the BPA content in the compositions obtained in the examples and comparative examples, and "BPA / hardener" represents the content of BPA relative to the hardener components (the total of imidazole-based compounds and tertiary amine compounds).

[0207] <Measuring device> LC: ACQUITY PREMIER (Waters) MS: Xevo TQ-XS (Waters) Column: L-kolumn ODS-3 (2.1 * 150 mm, 3 μm) <Measuring conditions> Solvent A: Acetonitrile Solvent B: 0.01% Aqueous ammonium acetate solution Column Temp.: 40 °C Flow: 0.4 mL / min A(%): 40 (0 min) - 40 (5 min) - 95 (8 min) - 95 (13 min) - 40 (13.1 min) - 23 (23 min) Injection vol: 1 μL <Mass Method> Ionization mode: ESI negative capillary: 2 kV Cone Source temp.: 150 °C Desolvation temperature: 500 °C Cone gas flow: 150 L / h Desolvation gas flow: 1000 L / h Collision gas flow: 0.15 mL / min Nebulizer gas flow: 7 bar Measurement mode: MRM BPA Cone: 25 V Collision: 29 eV Transition: 227.0 / 133.0, 210.9 BPA-d 16 Cone: 22 V Collision: 32 eV Transition: 241.0 / 142.0

[0208] 2. Storage stability The curing agent compositions of the examples and comparative examples were evaluated by the thickening rate (viscosity change rate) from the initial stage when stored (left standing) in a container at 40 °C for 30 days using an E-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.). Specifically, each curing agent composition was formulated according to the formulation described below to prepare an evaluation composition. For the evaluation composition immediately after preparation, the initial viscosity at 25 °C was obtained by measuring for 3 minutes at a rotational speed of 5 rpm using an E-type rotational viscometer. In addition, each of the above evaluation compositions was placed in a sealed container and stored at 40 °C for 30 days, then cooled to 25 °C, and in the same manner as the initial viscosity, measured for 5 minutes at a rotational speed of 5 rpm using an E-type rotational viscometer to obtain the viscosity after 30 days. Using the obtained initial viscosity and viscosity after 30 days, the thickening rate was calculated according to the following formula (A) and evaluated according to the following evaluation criteria. The results are shown in Table 1 below. Thickening rate (%) = [(viscosity after 30 days) ÷ initial viscosity] × 100 (A)

[0209] <Evaluation criteria> ◎: The thickening rate is 100% or more and 300% or less. Good: The viscosity increase rate is more than 300% and less than 500%. △: The viscosity increase rate is more than 500% and less than 1,000%. ×: The viscosity increase rate is more than 1,000%. It can be determined that the smaller the viscosity increase rate is, the more excellent the storage stability of the curing agent composition is. The curing agent compositions obtained in the examples and comparative examples were mixed according to the following formulas to obtain compositions for evaluation. The numerical values ​​in the formulas below represent parts by mass.

[0210] <Composition for evaluation> The above composition: 20 parts by weight Epoxy compound (ADEKA EP-4100E (bisphenol A type epoxy resin, molecular weight, epoxy equivalent 190)): 100 parts by weight

[0211] 3. Low temperature curing (thiol curing system) The curability of the compositions of the Examples and Comparative Examples in a thiol curing system was evaluated by differential scanning calorimetry (DSC measurement). Specifically, the evaluation compositions prepared in "2. Storage stability" were subjected to DSC measurement to confirm the peak top temperatures and were evaluated according to the following evaluation criteria. The results are shown in Tables 1 and 2 below. The peak top indicates the temperature at which the maximum heat release is observed within the scanning range. The lower the peak top temperature, the better the low-temperature curing property.

[0212] <Composition for evaluation> The above composition: 2 parts by mass Thiol compound (TS-G manufactured by Shikoku Kasei Corporation: 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril): 50 parts by mass Epoxy compound (ADEKA EP-4100E (bisphenol A type epoxy resin, molecular weight, epoxy equivalent 190)): 100 parts by weight

[0213] <Evaluation criteria> ⊚: The peak top temperature is 80°C or higher and 90°C or lower. 〇: The temperature at the peak top is over 90°C and 100°C or less. △: The temperature at the peak top is over 100°C and 110°C or less. ▽: The temperature at the peak top is over 110°C and 120°C or less. ×: The temperature at the peak top is over 120°C.

[0214] 4. Curing property (epoxy curing system) The curing property of the compositions of the examples and comparative examples in the epoxy curing system was evaluated by differential scanning calorimetry (DSC measurement). Specifically, as the evaluation composition, DSC measurement was performed in the same manner as in "3. Low-temperature curing property (thiol curing system)" except that the following composition was used, the temperature at the peak top was confirmed, and evaluation was performed according to the following evaluation criteria. The results are shown in Tables 1 to 2 below. Note that it can be judged that the lower the temperature at the peak top, the better the curing property. <Evaluation composition> · The above composition: 20 parts by mass · Epoxy compound (EP-4100E manufactured by ADEKA Corporation (bisphenol A type epoxy resin, molecular weight, epoxy equivalent 190)): 100 parts by mass

[0215] <DSC measurement conditions> · Measuring instrument: · Heating rate: 10°C / min · Scanning temperature range: 20°C ⇒ 300°C

[0216] <Evaluation criteria> ◎: The temperature at the peak top is 120°C or more and 130°C or less. 〇: The temperature at the peak top is over 130°C and 140°C or less. △: The temperature at the peak top is over 140°C and 150°C or less. ▽: The temperature at the peak top is over 150°C and 160°C or less. ×: The temperature at the peak top is over 160°C.

[0217]

Table 1

[0218]

Table 2

[0219] From the results in Tables 1 and 2, it was confirmed that the compositions of the examples were excellent in low-temperature curability. Also, it was confirmed that the compositions of the examples were excellent in storage stability. From the above, it was confirmed that the compositions of the examples were excellent in both low-temperature curability and storage stability. Also, from the results in Tables 1 and 2, it was confirmed that the compositions of the examples were excellent in curability even in an epoxy curing system not containing a thiol compound. Thus, it was confirmed that the compositions of the examples were excellent in low-temperature curability in both the thiol curing system and the epoxy curing system.

Claims

1. an imidazole-based compound including at least one of an imidazole compound and a modified imidazole compound; A tertiary amine compound other than the imidazole-based compound; A composition comprising: The tertiary amine compound is a primary amine compound having only a tertiary amino group as an amino group; a secondary amine compound having a tertiary amino group and at least one of a primary amino group and a secondary amino group; A tertiary amine compound which is a derivative of the secondary amine compound. Contains at least one selected from a total content of the second amine compound constituting the first amine compound, the second amine compound, and the tertiary amine compound is 10 parts by mass or more and 45 parts by mass or less in 100 parts by mass of the imidazole compound and the tertiary amine compound in total.

2. 2. The composition according to claim 1, wherein a total content of the second amine compound constituting the first amine compound, the second amine compound, and the tertiary amine compound is 5 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the composition.

3. The composition of claim 1 , wherein the imidazole-based compound comprises a modified imidazole compound.

4. The composition of claim 1 , wherein the tertiary amino group comprises a dihydrocarbon amino group.

5. The composition of claim 3, wherein the number of dihydrocarbylamino groups in the tertiary amine compound is 1 or more and 5 or less.

6. 2. The composition of claim 1, wherein the second amine compound that constitutes the first amine compound, the second amine compound, and the tertiary amine compound comprises an aliphatic compound.

7. 2. The composition of claim 1, wherein the tertiary amine compound is a reaction product of the secondary amine compound and an epoxy compound.

8. The composition of claim 1 , wherein the composition comprises a phenolic resin.

9. The composition of claim 1 , wherein the composition contains bisphenol A.

10. The composition according to claim 9, wherein the content of the bisphenol A is 1 ppm or more and 30,000 ppm or less based on the total content of the imidazole compound and the tertiary amine compound.

11. an imidazole-based compound including at least one of an imidazole compound and a modified imidazole compound; A tertiary amine compound other than the imidazole-based compound; A thiol compound, A composition comprising: The tertiary amine compound is a primary amine compound having only a tertiary amino group as an amino group; a secondary amine compound having a tertiary amino group and at least one of a primary amino group and a secondary amino group; and A tertiary amine compound which is a derivative of the secondary amine compound. Contains at least one selected from a total content of the second amine compound constituting the first amine compound, the second amine compound, and the tertiary amine compound is 10 parts by mass or more and 45 parts by mass or less in 100 parts by mass of the imidazole compound and the tertiary amine compound in total.

12. an imidazole-based compound including at least one of an imidazole compound and a modified imidazole compound; A tertiary amine compound other than the imidazole-based compound; A curable compound; A curable composition comprising: The tertiary amine compound is a primary amine compound having only a tertiary amino group as an amino group; a secondary amine compound having a tertiary amino group and at least one of a primary amino group and a secondary amino group; A tertiary amine compound which is a derivative of the secondary amine compound. Contains at least one selected from a total content of the second amine compounds constituting the first amine compound, the second amine compound, and the tertiary amine compound is 10 parts by mass or more and 45 parts by mass or less in 100 parts by mass of the imidazole compound and the tertiary amine compound in total.

13. The curable composition of claim 12 , wherein the curable composition comprises a thiol compound.

14. A cured product of the curable composition according to claim 12.

15. A method for producing a cured product, comprising a heating step of heating the curable composition according to claim 12.

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