Curing agent material, curing agent, curable composition, cured product, and method for producing cured product

Abstract

Provided is a curing agent material containing a compound that contains a structural unit having a tertiary amine structure group, and that has a weight-average molecular weight of 5,000 to 30,000.

Description

Curing agent material, curing agent, curable composition, cured product, and method for producing the cured product

[0001] The present disclosure relates to hardener materials.

[0002] In order to improve the low-temperature curing properties of an epoxy-based curable composition, multiple components may be used in combination as a curing agent. For example, Patent Documents 1 and 2 disclose the use of a urea derivative in combination with dicyandiamide as a curing accelerator. Patent Document 3 also discloses the use of a sulfonamide or the like in combination with imidazole as a curing accelerator.

[0003] Patent No. 3761919 Patent No. 3563154 Patent No. 4843256

[0004] However, the curing agent described in Patent Document 1 and the like has a problem in that it may have insufficient storage stability.

[0005] The present disclosure has been made in consideration of the above problems, and aims to provide a curing agent material capable of forming a curing agent having excellent low-temperature curing properties and storage stability.

[0006] As a result of intensive research to solve the above problems, the present inventors have found that a curing agent material containing a compound with a specific structure can form a curing agent with excellent low-temperature curing properties and storage stability, and have arrived at the present disclosure.

[0007] That is, the present disclosure provides a curing agent material characterized by containing a compound that includes a constitutional unit having a tertiary amine structural group and has a weight-average molecular weight of 5,000 or more and 30,000 or less.

[0008] According to the present disclosure, it is possible to provide a curing agent material capable of forming a curing agent having excellent low-temperature curing properties and storage stability.

[0009] The curing agent material of the present disclosure is preferably used in combination with an anionic curing agent, because the curing agent material can more effectively exhibit the effect of forming a curing agent having excellent low-temperature curing properties and storage stability.

[0010] In the present disclosure, the tertiary amine structural group preferably has a tertiary amino group, because this makes it easier to form a curing agent having excellent low-temperature curing properties and storage stability from the curing agent material.

[0011] In the present disclosure, the structural unit having the tertiary amine structural group preferably has at least one of a hydroxyl group and a carboxyl group, because this facilitates the formation of a curing agent having excellent low-temperature curing properties and storage stability.

[0012] In the present disclosure, the structural unit having a tertiary amine structural group preferably has a structural unit represented by the following general formula (100): This is because the curing agent material can easily form a curing agent having excellent low-temperature curing properties and storage stability.

[0013]

[0014] (In the formula, R 101 and R 102 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from Group B below; 1 is -O-, -CO-, -CO-O-, -O-CO-, -CO-NR 103 - and -NR 103 represents a divalent group selected from —CO—; 103 represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from the following group B; 2 represents a (c+1)-valent hydrocarbon group having 1 to 20 carbon atoms or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from the following group B, 1 represents a tertiary amine structural group; Group B represents -O-, -CO-, -CO-O-, -O-CO-, -NH-, -NHCO-, and -S-; a represents an integer of 0 or 1; b represents an integer of 0 or 1; and c represents an integer of 1 to 10.

[0015] In the present disclosure, the content of the structural unit having a tertiary amine structural group is preferably 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the compound, because the curing agent material can easily form a curing agent having excellent low-temperature curing properties and storage stability.

[0016] In the present disclosure, the compound preferably has, as a constituent unit other than the constituent unit having the tertiary amine structural group, a constituent unit derived from at least one compound selected from the group consisting of a hydroxyl group-containing ethylenically unsaturated compound, a carboxyl group-containing ethylenically unsaturated compound, and an aromatic unsaturated compound, because the curing agent material can easily form a curing agent having excellent low-temperature curing properties and storage stability.

[0017] The present disclosure provides a curing agent characterized by containing a compound that includes a constitutional unit having a tertiary amine structural group and has a weight average molecular weight of 5,000 or more and 30,000 or less, and an anionic curing agent.

[0018] According to the present disclosure, it is possible to provide a curing agent that has excellent low-temperature curing properties and storage stability.

[0019] In the present disclosure, the anionic curing agent preferably contains an amine-based curing agent, because the curing agent has superior low-temperature curing properties and storage stability.

[0020] The present disclosure provides a curable composition characterized by containing a compound that includes a structural unit having a tertiary amine structural group and has a weight-average molecular weight of 5,000 or more and 30,000 or less, and a curable compound.

[0021] According to the present disclosure, it is possible to provide a curable composition that has excellent low-temperature curing properties and storage stability.

[0022] The curable composition of the present disclosure preferably contains an anionic curing agent, because the curable composition has better low-temperature curing properties and storage stability.

[0023] The present disclosure provides a cured product of the above-described curable composition.

[0024] According to the present disclosure, by using the above-described curable composition, it is possible to provide a cured product that is easy to form.

[0025] The present disclosure provides a method for producing a cured product, comprising the step of heating the above-described curable composition.

[0026] According to the present disclosure, by using the above-described curable composition, it is possible to provide a method for producing the cured product, which allows the cured product to be easily formed.

[0027] The present disclosure provides a method for producing a curing agent material, characterized by comprising a reaction step of reacting a polymer having a weight average molecular weight of 3,000 or more and 25,000 or less, which has a bonding functional group b that is at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, and an amino group, with a compound having a bonding functional group c that can react with the bonding functional group b to form a covalent bond and a tertiary amine structural group.

[0028] The present disclosure provides a method for producing a curing agent material, wherein the polymer has, as the constituent unit having the bonding functional group b, a constituent unit derived from an unsaturated dicarboxylic acid or an unsaturated dicarboxylic acid anhydride.

[0029] According to the present disclosure, it is possible to provide a curing agent material capable of forming a curing agent having excellent low-temperature curing properties and storage stability.

[0030] The present disclosure relates to a curing agent material, a curing agent, a curable composition, a cured product, and a method for producing the cured product. The present disclosure is described in detail below.

[0031] A. Curing Agent Material First, the curing agent material of the present disclosure will be described. The curing agent material of the present disclosure is characterized in that it contains a structural unit having a tertiary amine structural group (hereinafter, may be referred to as structural unit A) and a compound (hereinafter, may be referred to as compound A) having a weight average molecular weight of 5,000 or more and 30,000 or less.

[0032] The curing agent material of the present disclosure can form a curing agent with excellent low-temperature curing properties and storage stability. The reason why such a curing agent can be formed is unclear, but is presumed to be as follows. Specifically, the compound A contained in the curing agent material has a structure in which a tertiary amine structural group, which is an active ingredient for curing acceleration, is bound to a polymer chain. At temperatures lower than the reaction temperature, the tertiary amine structural group exists in a state of being enclosed by the polymer chain due to intermolecular forces such as hydrogen bonding with atoms in the polymer chain and van der Waals interactions. Furthermore, under conditions in which such intermolecular forces exist, the molecular motion of the polymer can be suppressed by having a polymer chain of a predetermined length. Therefore, by having a weight-average molecular weight within a predetermined range, compound A has low fluidity until the predetermined temperature is reached, and the tertiary amine structural group can be maintained in a state of being stably enclosed in the polymer chain. Furthermore, the presence of such intermolecular forces reduces the nucleophilicity of the tertiary amine, thereby suppressing the curing acceleration effect of the tertiary amine structural group contained in compound A itself until the predetermined temperature range is reached. Furthermore, when compound A is used in combination with an anionic curing agent, the manifestation of the curing-accelerating effect of the anionic curing agent can be suppressed. Furthermore, by having a weight-average molecular weight within a predetermined range, compound A can, for example, improve compatibility and diffusibility with the curable compound used in combination when heated and its fluidity increases, thereby enabling the curing of the curable compound or the curing-accelerating effect of the anionic curing agent to be manifested without impairing its curability. Furthermore, compound A has a structure in which multiple tertiary amine structural groups are bonded, and therefore the density of the tertiary amine structural groups is high. As a result, once a curing reaction caused by the tertiary amine structural groups begins to occur, a chain reaction is likely to proceed, making it possible to achieve lower temperature curing with a small amount added. Furthermore, when compound A is used in combination with an anionic curing agent, when the temperature reaches a predetermined temperature range and the fluidity of compound A increases, the densely arranged tertiary amine structural groups can improve the compatibility of the anionic curing agent in the curable composition. As a result, when the anionic curing agent is in a solid state, its melting point can be lowered, making it easier to manifest curability at lower temperatures than when the anionic curing agent is used alone.From the above, by including Compound A in the curing agent material, it becomes easy to form a curing agent that is excellent in both low-temperature curing properties and storage stability.

[0033] The curing agent material of the present disclosure contains Compound A. Hereinafter, each component of the curing agent material of the present disclosure will be described in detail.

[0034] 1. Compound A Compound A is a compound that includes a structural unit having a tertiary amine structural group (hereinafter, may be referred to as structural unit A) and has a weight average molecular weight of 5,000 or more and 30,000 or less.

[0035] (1) Weight-average molecular weight The weight-average molecular weight of compound A may be from 5,000 to 30,000, preferably from 7,000 to 25,000, more preferably from 9,000 to 22,000, even more preferably from 11,000 to 20,000, particularly preferably from 13,000 to 18,000, and most preferably from 15,000 to 17,000. When the weight-average molecular weight is within the above range, the curing agent material has excellent low-temperature curing properties and storage stability.

[0036] The weight-average molecular weight may be measured by any method as long as it can accurately measure the weight-average molecular weight of Compound A. For example, the weight-average molecular weight can be determined as a standard polystyrene-equivalent value by GPC (gel permeation chromatography), and can be measured, for example, under the following conditions:

[0037] <Measurement conditions> GPC apparatus: HLC-8320GPC (manufactured by Tosoh Corporation) Solvent: DMF (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) / 10 mM LiBr solution Flow rate: 0.6 mL / min Column: TSKgel guard column Super AW-H (4.6 mm I.D. × 3.5 cm) × 1 + TSKgel Super AWM-H (6.0 mm I.D. × 15 cm) × 2 (manufactured by Tosoh Corporation) As column pretreatment, a DMF / 100 mM triethylamine solution was passed through the column before measurement to mask the adsorption points in advance. Column temperature: 40°C Sample concentration: 1 mg / mL Injection volume: 20 μL Polystyrene standards for calibration curve: Mw 5,480,000, 1,090,000, 427,000, 96,400, 37,900, 10,200, 2,550, 598 (manufactured by Tosoh)

[0038] (2) Structural Unit Having a Tertiary Amine Structural Group The structural unit A has a tertiary amine structural group. A tertiary amine structure refers to a structure in which three bonds of a nitrogen atom form covalent bonds with hydrocarbon carbon atoms. Therefore, if the carbon atom to which a nitrogen atom is bonded is a carbonyl group, that is, if it forms an amide group, a urea structure, a urethane structure, or the like together with the nitrogen atom, it does not fall under the category of a tertiary amine structure. Examples of such tertiary amine structural groups include cyclic tertiary amino groups in which the nitrogen atom constituting the tertiary amine structure is included as a ring-constituting atom, tertiary amino groups in which the nitrogen atom constituting the tertiary amine structure is not included as a ring-constituting atom, and groups combining the cyclic tertiary amino group and the tertiary amino group. In the present disclosure, the tertiary amine structural group preferably has the tertiary amino group, and more preferably is a tertiary amino group. This is because the curing agent material facilitates the formation of a curing agent with excellent low-temperature curing properties and storage stability.

[0039] The tertiary amino group may be a group in which two hydrogen atoms of an amino group (-NH2) are substituted with hydrocarbon groups, for example, a group represented by the following general formula (1):

[0040]

[0041] (In the formula, R1 and R 2 each independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from the following Group A, * represents a bond, and Group A includes -O-, -CO-, -CO-O-, -O-CO-, -NR 11 represents CO- and -S-; R 11 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0042] Examples of the hydrocarbon group having 1 to 20 carbon atoms include an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms.

[0043] The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a hydrocarbon group that does not contain an aromatic hydrocarbon ring or a heterocycle, and examples thereof include a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aliphatic ring-containing group 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.

[0044] 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 groups. Examples of the branched alkyl group include an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an isopentyl group, a tert-pentyl group, a 2-hexyl group, a 3-hexyl group, a 2-heptyl group, a 3-heptyl group, an isoheptyl group, a tert-heptyl group, an isooctyl group, a tert-octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a hebrotadecyl group, and an octadecyl group.

[0045] 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 internal unsaturated bond. Examples of terminal alkenyl groups include vinyl, allyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, and 5-hexenyl. Examples of internal alkenyl groups include 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, and 4,8,12-tetradecatrienylallyl.

[0046] Examples of the cycloalkyl group having 3 to 20 carbon atoms include saturated monocyclic alkyl groups having 3 to 20 carbon atoms, saturated polycyclic alkyl groups having 3 to 20 carbon atoms, and groups having 4 to 20 carbon atoms in which one or more hydrogen atoms in the ring of these groups have been substituted with an alkyl group. Examples of the saturated monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. Examples of the saturated polycyclic alkyl group include an adamantyl group, a decahydronaphthyl group, an octahydropentalene group, and a bicyclo[1.1.1]pentanyl group. Examples of the alkyl group substituting a hydrogen atom in the ring of a saturated monocyclic or saturated polycyclic alkyl group include the groups exemplified above as the alkyl group having 1 to 20 carbon atoms. Examples of the group in which one or more hydrogen atoms in the ring of a saturated polycyclic alkyl group have been substituted with an alkyl group include a bornyl group.

[0047] The cycloalkylalkyl group having 4 to 20 carbon atoms refers to a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. Examples of cycloalkylalkyl groups having 4 to 20 carbon atoms and 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 cycloalkylalkyl groups having 4 to 20 carbon atoms and in which the cycloalkyl group is polycyclic include a 3-3-adamantylpropyl group and a decahydronaphthylpropyl group.

[0048] The aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms is a hydrocarbon group that contains an aromatic hydrocarbon ring but does not contain a heterocycle, and may have an aliphatic hydrocarbon structure. Examples of such aromatic hydrocarbon ring-containing groups include aryl groups having 6 to 20 carbon atoms and arylalkyl groups having 7 to 20 carbon atoms.

[0049] The aryl group having 6 to 20 carbon atoms may have a monocyclic structure, a fused ring structure, or two linked aromatic hydrocarbon rings. The aryl group having two linked aromatic hydrocarbon rings may be two linked aromatic hydrocarbon rings having a monocyclic structure, a linked aromatic hydrocarbon ring having a monocyclic structure and a linked aromatic hydrocarbon ring having a fused ring structure, or a linked aromatic hydrocarbon ring having a fused ring structure and an linked aromatic hydrocarbon ring having a fused ring structure. The linking group connecting the two aromatic hydrocarbon rings may be any group that can impart aromaticity to the aryl group as a whole, and examples thereof include a single bond, a sulfide group (—S—), and a carbonyl group. The aryl group may include not only a group in which one hydrogen atom has been removed from an aromatic hydrocarbon ring (hereinafter sometimes referred to as an aromatic ring group), but also a group in which one or more hydrogen atoms in the aromatic ring group have been substituted with a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 15 carbon atoms. Examples of aryl groups having a single ring structure include a phenyl group; and alkylphenyl groups such as a tolyl group, a xylyl group, an ethylphenyl group, and a 2,4,6-trimethylphenyl group. Examples of aryl groups having a fused ring structure include a naphthyl group, an anthracenyl group, a phenanthryl group, and a pyrenyl group. Examples of aryl groups having two linked single-ring aromatic hydrocarbon rings include a biphenyl group, a diphenyl sulfide group, and a benzoylphenyl group.

[0050] The arylalkyl group having 7 to 20 carbon atoms refers to a group in which one or more hydrogen atoms in an 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.

[0051] In the present disclosure, a substituted hydrocarbon group refers to a hydrocarbon group in which a hydrogen atom is substituted with a substituent, such as a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, or an amino group.

[0052] A hydrocarbon group in which one or more methylene groups have been substituted with a divalent group selected from Group A does not have a structure in which multiple divalent groups are adjacent to each other. The multiple divalent groups may be the same or different.

[0053] Examples of the hydrocarbon group having 1 to 10 carbon atoms include an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon ring-containing group having 6 to 10 carbon atoms.

[0054] The aliphatic hydrocarbon group having 1 to 10 carbon atoms may be a hydrocarbon group that does not contain an aromatic hydrocarbon ring or a heterocycle, and examples thereof include a chain aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aliphatic ring-containing group having 3 to 10 carbon atoms. Examples of the chain aliphatic hydrocarbon group having 1 to 10 carbon atoms include an alkyl group having 1 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms. Examples of the aliphatic ring-containing group having 3 to 10 carbon atoms include a cycloalkyl group having 3 to 10 carbon atoms and a cycloalkylalkyl group having 4 to 10 carbon atoms.

[0055] The alkyl group having 1 to 10 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, and decyl.

[0056] The alkenyl group having 2 to 10 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 internal unsaturated bond. Examples of terminal alkenyl groups include vinyl, allyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, and 5-hexenyl. Examples of internal alkenyl groups include 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, and 4-decenyl.

[0057] Examples of the cycloalkyl group having 3 to 10 carbon atoms include saturated monocyclic alkyl groups having 3 to 10 carbon atoms, saturated polycyclic alkyl groups having 3 to 10 carbon atoms, and groups having 4 to 10 carbon atoms in which one or more hydrogen atoms in the ring of these groups have been substituted with an alkyl group. Examples of the saturated monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. Examples of the saturated polycyclic alkyl group include an adamantyl group, a decahydronaphthyl group, an octahydropentalene group, and a bicyclo[1.1.1]pentanyl group. Examples of the alkyl group substituting a hydrogen atom in the ring of a saturated monocyclic or saturated polycyclic alkyl group include the groups exemplified above as the alkyl group having 1 to 10 carbon atoms. Examples of groups in which one or more hydrogen atoms in the ring of a saturated polycyclic alkyl group have been substituted with an alkyl group include a bornyl group.

[0058] The cycloalkylalkyl group having 4 to 10 carbon atoms refers to a group having 4 to 10 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. Examples of cycloalkylalkyl groups having 4 to 10 carbon atoms and 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, and a cyclooctylmethyl group. Examples of cycloalkylalkyl groups having 4 to 10 carbon atoms and in which the cycloalkyl group is polycyclic include a norbornylethyl group and an isonorbornylethyl group.

[0059] The aromatic hydrocarbon ring-containing group having 6 to 10 carbon atoms is a hydrocarbon group that contains an aromatic hydrocarbon ring but does not contain a heterocycle, and may have an aliphatic hydrocarbon structure. Examples of such aromatic hydrocarbon ring-containing groups include aryl groups having 6 to 10 carbon atoms and arylalkyl groups having 7 to 10 carbon atoms.

[0060] The aryl group having 6 to 10 carbon atoms may have a monocyclic structure or a fused ring structure. 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, or a 2,4,6-trimethylphenyl group; and the like. Examples of the aryl group having a fused ring structure include a naphthyl group.

[0061] The arylalkyl group having 7 to 10 carbon atoms refers to a group in which one or more hydrogen atoms in an alkyl group are substituted with an aryl group. Examples of the arylalkyl group having 7 to 10 carbon atoms include a benzyl group, an indenyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, and a phenylethyl group.

[0062] In the present disclosure, the number of carbon atoms is R 1 , R 2and the like, and when a hydrogen atom in the hydrocarbon group is substituted with a substituent, it specifies the number of carbon atoms of the hydrocarbon group after the substitution. For example, in the case of "a group in which the hydrogen atom of a C10 alkyl group is substituted with a substituent," the number of carbon atoms 10 refers to the number of carbon atoms in "the alkyl group after the hydrogen atom is substituted with a substituent," not the number of carbon atoms in the alkyl group before the hydrogen atom is substituted. Furthermore, in the present disclosure, the number of carbon atoms in a group in which a methylene group in a hydrocarbon group is substituted with a divalent group refers to the number of carbon atoms in the group after the substitution. For example, in the case of "a group in which the methylene group in a C10 alkyl group is substituted with a divalent group," the number of carbon atoms 10 refers to the number of carbon atoms in "the alkyl group after the methylene group is substituted with a divalent group," not the number of carbon atoms in the alkyl group before the substitution.

[0063] R 1 and R 2 are each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a group in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from Group A above, and are preferably substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, and more preferably unsubstituted hydrocarbon groups having 1 to 20 carbon atoms. This is because the above curing agent material facilitates the formation of a curing agent with excellent low-temperature curing properties and storage stability. In the present disclosure, R 1 and R 2 The hydrocarbon group used in may be linear or branched, but is preferably linear. This is because the curing agent material can easily form a curing agent with excellent low-temperature curing properties and storage stability. 1 and R 2 The number of carbon atoms in each of the groups is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and even more preferably 1 or more and 3 or less, and is 1 or 2 (i.e., R 1 and R 2 is a dimethylamino group or a diethylamino group), and is 1 (i.e., R 1 and R 2is a dimethylamino group), because the above curing agent material can easily form an excellent curing agent due to its low-temperature curing property and storage stability.

[0064] The cyclic tertiary amino group may be any group containing a nitrogen atom constituting a tertiary amine structure as a ring-constituting atom, and the ring-constituting atom serving as a bond. The ring-constituting atom serving as a bond may be a nitrogen atom or a carbon atom.

[0065] Examples of such cyclic tertiary amino groups include quinuclidine groups, imidazole groups, pyrazole groups, triazole groups, imidazoline groups, tetrazole groups, triethylenediamine groups, N-substituted morpholine groups obtained by removing one hydrogen atom from an N-substituted morpholine ring, N-substituted piperidine groups obtained by removing one hydrogen atom from the piperidine ring of an N-substituted piperidine ring, N-substituted piperazine groups obtained by removing one hydrogen atom from the piperazine ring of an N-substituted piperazine ring, and N,N-substituted piperazine groups obtained by removing one hydrogen atom from the piperazine ring of an N,N-substituted piperazine ring. Here, "N-substituted" means that a hydrogen atom bonded to a nitrogen atom constituting a cyclic secondary amine structure is substituted with a hydrocarbon group to form a cyclic tertiary amine structure. "N,N-substituted" means that a hydrogen atom bonded to each of two nitrogen atoms constituting a cyclic secondary amine structure is substituted with a hydrocarbon group to form two cyclic tertiary amine structures.

[0066] Examples of the group combining a cyclic tertiary amino group and a tertiary amino group include a group combining two cyclic tertiary amino groups, a group combining two tertiary amino groups, and a group combining a cyclic tertiary amino group and a tertiary amino group. Examples of the group combining two cyclic tertiary amino groups include a group in which one or more hydrogen atoms in a cyclic tertiary amino group are substituted with the cyclic tertiary amino group. Examples of the group combining two tertiary amino groups include a group in which one or more hydrogen atoms in a tertiary amino group are substituted with the tertiary amino group. Examples of the group combining a cyclic tertiary amino group and a tertiary amino group include a group in which one or more hydrogen atoms in a tertiary amino group are substituted with the cyclic tertiary amino group, and a group in which one or more hydrogen atoms in a cyclic tertiary amino group are substituted with the tertiary amino group.

[0067] The structure of the repeating portion of the structural unit A may be any structure such as a structure derived from an ethylenically unsaturated compound, a polyester structure, a polyurethane structure, a polyether structure, or a polycarbonate structure, and structural units of different structures may be combined.

[0068] In the present disclosure, it is preferable that the structure of the repeating portion of the structural unit A has a structure derived from an ethylenically unsaturated compound, because the above curing agent material facilitates the formation of a curing agent that is excellent in low-temperature curing properties and storage stability.

[0069] The structural unit A has a tertiary amine structural group, but may also have a functional group other than the tertiary amine structural group. Examples of such functional groups include halogen atoms, cyano groups, nitro groups, hydroxyl groups, thiol groups, and carboxyl groups. In the present disclosure, the other functional group preferably has at least one of a hydroxyl group and a carboxyl group, and more preferably a carboxyl group. This is because the curing agent material facilitates the formation of a curing agent with excellent low-temperature curing properties and storage stability, and in particular, excellent storage stability. While the reason why the inclusion of the other functional group results in a curing agent material with excellent low-temperature curing properties and storage stability, particularly excellent storage stability, is not clear, it is presumed as follows. That is, the nitrogen atom constituting the tertiary amine structure contained in the structural unit A and the other functional group interact through hydrogen bonds, ionic bonds, etc., thereby suppressing the molecular motion of the compound A itself and making it easier to further reduce fluidity. As a result, it becomes easier to maintain the compound A in a solid state, and the curing-accelerating effect can be more easily suppressed until the temperature reaches a predetermined range. For this reason, the above-mentioned hardener material makes it easy to form a hardener having excellent storage stability.

[0070] When the repeating portion of the structural unit A has a structure derived from an ethylenically unsaturated compound, the bonding position of the other functional group may be the same carbon atom as the carbon atom to which the tertiary amine structural group is bonded, among the two carbon atoms derived from the ethylenically unsaturated compound constituting the repeating portion. However, it is preferable that the other functional group be bonded to a different carbon atom, i.e., the tertiary amine structural group is bonded to one of the two carbon atoms derived from the ethylenically unsaturated compound constituting the repeating portion, and the other functional group is bonded to the other carbon atom. This is because the curing agent material facilitates the formation of a curing agent with excellent low-temperature curing properties and storage stability. Note that "bonded to the tertiary amine structural group" does not necessarily mean that the tertiary amino group, cyclic tertiary amino group, etc. constituting the tertiary amine structural group are directly bonded, but also includes cases where they are indirectly bonded via another atom. Similarly, the phrase "bonded to the other functional group" does not necessarily mean that the other functional group is directly bonded, but also includes cases where it is indirectly bonded via another atom.

[0071] The structural unit A preferably has a structural unit represented by the following general formula (100): This is because the above curing agent material facilitates the formation of a curing agent that has excellent low-temperature curing properties and storage stability.

[0072]

[0073] (In the formula, R 101 and R 102 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from Group B below; 1 is -O-, -CO-, -CO-O-, -O-CO-, -CO-NR 103 - and -NR 103 represents a divalent group selected from —CO—; 103 represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from the following group B;2 represents a (c+1)-valent hydrocarbon group having 1 to 20 carbon atoms or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from the following group B, 1 represents a tertiary amine structural group; Group B represents -O-, -CO-, -CO-O-, -O-CO-, -NH-, -NHCO-, and -S-; a represents an integer of 0 or 1; b represents an integer of 0 or 1; and c represents an integer of 1 to 10.

[0074] R 101 and R 102 The hydrocarbon group having 1 to 20 carbon atoms used in R 1 The hydrocarbon group R can be the same as that described above, and therefore the explanation will be omitted here. 103 The hydrocarbon group having 1 to 10 carbon atoms used in R 11 The hydrocarbon group may be the same as that described above for the hydrocarbon group used in the above, and therefore, the description thereof will be omitted here.

[0075] L 2 The c+1-valent hydrocarbon group used in R 1 Examples of the hydrocarbon groups usable in the above formula (1) include groups in which c hydrogen atoms have been removed.

[0076] The above R 101 is preferably a hydrogen atom, a hydroxyl group, or a carboxyl group, more preferably a hydroxyl group or a carboxyl group, and even more preferably a carboxyl group, because the above curing agent material facilitates the formation of a curing agent with excellent low-temperature curing properties and storage stability.

[0077] The above R 102is preferably a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from Group B above, more preferably a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from Group B above, even more preferably a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom or an unsubstituted hydrocarbon group having 1 to 3 carbon atoms, and most preferably a hydrogen atom. This is because the above curing agent material facilitates the formation of a curing agent that has excellent low-temperature curing properties and storage stability.

[0078] The above L 1 is -O-, -CO-, -CO-O-, -O-CO-, -CO-NR 103 - and -NR 103 The divalent group is selected from -CO-, preferably a divalent group selected from -CO-, -CO-O-, and -O-CO-, more preferably -CO- or -CO-O-, and even more preferably -CO-O-. This is because the above curing agent material facilitates the formation of a curing agent with excellent low-temperature curing properties and storage stability. 1 In the -CO-O- used in the above, "CO" is bonded to a carbon atom constituting the repeating portion of the structural unit A, and "O" is bonded to L. 2 "CO" in -O-CO-, -CO-NR 103 -'s "NR 103 " and -NR 103 The "CO" in -CO- is also L 2 represents binding to

[0079] c is L 2 X bonded to 1 The number of groups represented by c is an integer of 1 to 10, preferably 1 to 5, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 3. This is because the above curing agent material facilitates the formation of a curing agent that is excellent in low-temperature curing property and storage stability.

[0080] L 2 The hydrocarbon group used in is preferably a c+1-valent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a c+1-valent aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, more preferably a c+1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a c+1-valent aromatic hydrocarbon ring-containing group having 6 to 15 carbon atoms, even more preferably a c+1-valent aliphatic hydrocarbon group having 1 to 5 carbon atoms or a c+1-valent aromatic hydrocarbon ring-containing group having 7 to 10 carbon atoms, and particularly preferably a c+1-valent aromatic hydrocarbon ring-containing group having 8 to 10 carbon atoms. This is because the above curing agent material facilitates the formation of a curing agent with excellent low-temperature curing properties and storage stability.

[0081] L 2 The (c+1)-valent aromatic hydrocarbon ring-containing group used in is preferably a group in which c hydrogen atoms have been removed from an aryl group or an arylalkyl group, more preferably a group in which c hydrogen atoms have been removed from an aryl group, and even more preferably a group in which c hydrogen atoms have been removed from an alkylphenyl group. This is because the above curing agent material facilitates the formation of a curing agent with excellent low-temperature curing properties and storage stability. When c is 3, L 2 The c+1-valent alkylphenyl group used in is preferably a trialkylphenyl group in which one hydrogen atom has been removed from each of the three alkyl groups, and more preferably a 2,4,6-trimethylphenyl group in which one hydrogen atom has been removed from each of the three methyl groups. This is because the above curing agent material facilitates the formation of an excellent curing agent due to its low-temperature curing properties and storage stability.

[0082] X 1 The preferred groups of the tertiary amine structural group are the same as those of the tertiary amine structural group, and therefore, the explanation thereof will be omitted here.

[0083] The structural unit A may be located in either the main chain or the side chain of the compound A, but is preferably located in the main chain, because the curing agent material described above facilitates the formation of an excellent curing agent due to its low-temperature curing properties and storage stability.

[0084] The content of the structural unit A is preferably from 1 to 99 parts by mass, more preferably from 30 to 70 parts by mass, even more preferably from 40 to 60 parts by mass, particularly preferably from 50 to 55 parts by mass, and most preferably from 52 to 55 parts by mass, per 100 parts by mass of compound A. This is because the above curing agent material facilitates the formation of a curing agent that is excellent in low-temperature curing properties and storage stability.

[0085] The content of the structural unit A is preferably 1 mol or more and 99 mol or less, more preferably 5 mol or more and 60 mol or less, even more preferably 10 mol or more and 50 mol or less, particularly preferably 15 mol or more and 40 mol or less, and most preferably 20 mol or more and 30 mol or less, per 100 mol of all structural units contained in compound A. This is because the above curing agent material facilitates the formation of a curing agent excellent in low-temperature curing property and storage stability.

[0086] The method for producing compound A may be any method capable of producing a compound having structural unit A. When the structure of the repeating portion of structural unit A is derived from an ethylenically unsaturated compound, such a production method may include a method using an ethylenically unsaturated compound having a bonding functional group b (hereinafter, sometimes referred to as compound B) and a compound having a functional group capable of reacting with the bonding functional group b to form a covalent bond (hereinafter, bonding functional group c) and a tertiary amine structural group (hereinafter, sometimes referred to as compound C). More specifically, examples include a method of homopolymerizing or copolymerizing a reaction product of compound B and compound C with another ethylenically unsaturated compound (hereinafter, sometimes referred to as method 1), a method of homopolymerizing or copolymerizing compound B with another ethylenically unsaturated compound, and then reacting compound C with the bonding functional group b derived from compound B, i.e., a method of reacting compound C with a polymer having a bonding functional group b (hereinafter, sometimes referred to as method 2), and the like. In the present disclosure, the production method may be either method 1 or method 2, but method 2 is preferred. This is because compound A can be easily produced.

[0087] Examples of the bonding functional group b include a hydroxyl group, a carboxyl group, an epoxy group, and an amino group. The carboxyl group as the bonding functional group b also includes a dicarboxylic acid anhydride structure. In this case, the dicarboxylic acid anhydride structure as the bonding functional group b may share a portion with the ethylenically unsaturated bond site. Examples of the compound B include a hydroxyl group-containing ethylenically unsaturated compound, a carboxyl group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, and an amino group-containing ethylenically unsaturated compound.

[0088] In the present disclosure, the bonding functional group b is preferably a hydroxyl group, a carboxyl group, or an amino group, more preferably a hydroxyl group or a carboxyl group, and even more preferably a carboxyl group. This is because the above-mentioned curing agent material facilitates the formation of an excellent curing agent due to its low-temperature curing properties and storage stability. That is, compound B is preferably a hydroxyl group-containing ethylenically unsaturated compound, a carboxyl group-containing ethylenically unsaturated compound, or an amino group-containing ethylenically unsaturated compound, more preferably a hydroxyl group-containing ethylenically unsaturated compound or a carboxyl group-containing ethylenically unsaturated compound, and even more preferably a carboxyl group-containing ethylenically unsaturated compound. This is because the above-mentioned curing agent material facilitates the formation of an excellent curing agent due to its low-temperature curing properties and storage stability.

[0089] Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate; polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above-mentioned hydroxyalkyl (meth)acrylates; and polyester mono(meth)acrylates obtained by addition of poly-γ-valerolactone, poly-ε-caprolactone, and / or poly-12-hydroxystearic acid.

[0090] Examples of carboxyl group-containing ethylenically unsaturated compounds include acrylic acid, methacrylic acid, crotonic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, and ethylene oxide-modified succinic acid (meth)acrylate, as well as adducts of the above hydroxyl group-containing ethylenically unsaturated compounds with carboxylic acid anhydrides, β-carboxyethyl (meth)acrylate, and ω-carboxypolycaprolactone (meth)acrylate, as well as unsaturated monocarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, as well as unsaturated dicarboxylic acids such as itaconic anhydride and maleic anhydride. In the present disclosure, the carboxyl group-containing ethylenically unsaturated compound is preferably an unsaturated dicarboxylic acid or an unsaturated dicarboxylic acid anhydride, more preferably an unsaturated dicarboxylic acid anhydride, and even more preferably maleic anhydride. This is because the above-mentioned curing agent material facilitates the formation of a curing agent with excellent low-temperature curing properties and storage stability, and also facilitates the addition of the tertiary amine structural group.

[0091] Examples of epoxy group-containing ethylenically unsaturated compounds include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate.

[0092] Examples of the amino group-containing ethylenically unsaturated compound include (meth)acrylamide, N-methoxymethyl-(meth)acrylamide, N-ethoxymethyl-(meth)acrylamide, N-propoxymethyl-(meth)acrylamide, N-butoxymethyl-(meth)acrylamide, and N-pentoxymethyl-(meth)acrylamide.

[0093] The binding functional group c is preferably a hydroxyl group, a carboxyl group, or an amino group, more preferably a hydroxyl group or a carboxyl group, and even more preferably a hydroxyl group, because the curing agent material has low-temperature curing properties and storage stability, making it easy to form a curing agent with excellent properties.

[0094] As the compound C, for example, a compound represented by the following general formula (2) can be used.

[0095]

[0096] (In the formula, R 12 represents a hydroxyl group, a carboxyl group, or an amino group; L 12 represents a d+1-valent hydrocarbon group having 1 to 20 carbon atoms or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from the following group C, 11 represents a tertiary amine structural group; Group C represents -O-, -CO-, -CO-O-, -O-CO-, -NH-, -NHCO-, and -S-; and d represents an integer of 1 to 10.

[0097] R 12 The amino group used in the present invention may be one having an active hydrogen group, such as a primary amino group (-NH2), a secondary amino group (-NHR 21 ) can be used. 21 For example, a hydrocarbon group having 1 to 10 carbon atoms can be used. As the hydrocarbon group having 1 to 10 carbon atoms, the above-mentioned R 11 The hydrocarbon group may be the same as that described above for the hydrocarbon group used in the above, and therefore, the description thereof will be omitted here.

[0098] L 12 The hydrocarbon group having 1 to 20 carbon atoms and a valence of d+1 used in R 1 Examples of such a hydrocarbon group include groups obtained by removing d hydrogen atoms from the hydrocarbon groups described above as the hydrocarbon groups used in the above. 12 The preferred groups of L 2 Since the preferred groups of the formula (I) can be the same as those described above, the explanation here will be omitted.

[0099] R 12 The preferred groups for the bonding functional group c are the same as those for the bonding functional group c, and therefore the explanation thereof will be omitted here.

[0100] X 11 The preferred groups of the tertiary amine structural group can be the same as the preferred groups of the tertiary amine structural group, and therefore, the explanation thereof will be omitted here.

[0101] The preferred range of d can be the same as the preferred range of c in the above general formula (100).

[0102] The molecular weight of compound C is preferably 50 or more and 2,000 or less, more preferably 100 or more and 1,000 or less, even more preferably 150 or more and 500 or less, and particularly preferably 200 or more and 300 or less, because this facilitates the synthesis of compound A.

[0103] Examples of such compound C in which d is 1 include 1-methyl-4-piperidinol (CAS Registry No. 106-52-5), 1-methyl-3-pyrrolidinol (CAS Registry No. 13220-33-2), 4-(hydroxymethyl)-1-methylpiperidine (CAS Registry No. 20691-89-8), 1-ethyl-3-pyrrolidinol (CAS Registry No. 30727-14-1), 4-(dimethylamino)-1-butanol (CAS Registry No. 13330-96-6), and 3-dimethylamino-1-propanol (CAS Registry No. 3179-6). 3-3), 2-dimethylaminoethanol (CAS Registry Number 108-01-0), 5-(dipropylamino)-1-pentanol (CAS Registry Number 39984-57-1), 2-(2-dimethylaminoethoxy)ethanol (CAS Registry Number 1704-62-7), 3-diethylamino-1-propanol (CAS Registry Number 622-93-5), 1-dimethylamino-2-propanol (CAS Registry Number 108-16-7), 3-(dimethylamino)-1-butanol (CAS Registry Number 2893-65-4), 2-dimethylamino-2-methyl -1-propanol (CAS Registry No. 7005-47-2), 2-[butyl(methyl)amino]ethanol (CAS Registry No. 2893-48-3), 2-(dibutylamino)ethanol (CAS Registry No. 102-81-8), 4-(diethylamino)-2-butyn-1-ol (CAS Registry No. 10575-25-4), (CAS Registry No.), 2-[ethyl(methyl)amino]-1-propanol (CAS Registry No. 1060817-16-4), (CAS Registry No.), tropine (CAS Registry No. 120-29-6), (1-ethylpyrrolidine- (1-isopropylpiperidin-4-yl)methanol (CAS Registry No. 61472-22-8), pseudotropine (CAS Registry No. 135-97-7), (1-isopropylpiperidin-4-yl)methanol (CAS Registry No. 280774-03-0), (1-isopropylpyrrolidin-3-yl)methanol (CAS Registry No. 2148-53-0), 3-quinuclidinol (CAS Registry No. 1619-34-7), 2-diethylaminoethanol (CAS Registry No. 100-37-8), 1-diethylamino-2-propanol (CAS Registry No. 4402-32-8),2-(Diisopropylamino)ethanol (CAS Registry Number 96-80-0), 5-diethylamino-1-pentanol (CAS Registry Number 2683-57-0), 3-(dimethylamino)-2,2-dimethyl-1-propanol (CAS Registry Number 19059-68-8), 1-methyl-3-piperidinol (CAS Registry Number 3554-74-3), 1-ethyl-3-piperidinol (CAS Registry Number 13444-24-1), 1-methyl 1-methyl-2-piperidinemethanol (CAS Registry No. 20845-34-5), 1-methyl-3-piperidinemethanol (CAS Registry No. 7583-53-1), 1-methyl-2-piperidineethanol (CAS Registry No. 533-15-3), [1-(2-methoxyethyl)piperidin-3-yl]methanol (CAS Registry No. 915921-51-6), 6-dimethylamino-1-hexanol (CAS Registry No. 1862-07-3), etc. aliphatic compounds, [(dimethylamino)methyl]phenol (CAS Registry No. 25338-55-0), hordenine (CAS Registry No. 539-15-1), 2-[(dimethylamino)methyl]phenol (CAS Registry No. 120-65-0), 2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol (CAS Registry No. 88-27-7), 2-(benzylmethylamino)ethanol (CAS Registry No. 101-98-4 ), 3-[1-(dimethylamino)ethyl]phenol (CAS Registry No. 105601-04-5), 3-diethylaminophenol (CAS Registry No. 91-68-9), 1-benzyl-3-piperidinol (CAS Registry No. 14813-01-5), 1-benzyl-4-piperidinol (CAS Registry No. 4727-72-4), 1-benzyl-3-pyrrolidinol (CAS Registry No. 775-15-5), and other aromatic compounds. As the compound C, compounds in which d is 2 include aliphatic compounds such as 2-(4-methylpiperazin-1-yl)cyclopentanol (CAS Registry Number 915921-53-8), 1,3-bis(dimethylamino)-2-propanol (CAS Registry Number 5966-51-8), and 1,4-diazabicyclo[2.2.2]octan-2-ylmethanol (CAS Registry Number). As the compound C, compounds in which d is 3 includeExamples of the compound C include aromatic compounds such as 2,4,6-tris(dimethylaminomethyl)phenol (CAS Registry Number 90-72-2). Examples of the compound C that can be used include aliphatic compounds such as 2-[[2-(dimethylamino)ethyl]methylamino]ethanol (CAS Registry Number 2212-32-0), 4-methylpiperazine-1-ethanol (CAS Registry Number 5464-12-0), and 1-bis[3-(dimethylamino)propyl]amino-2-propanol (CAS Registry Number 67151-63-7).

[0104] (3) Structural Unit B Compound A can have a structural unit other than structural unit A (hereinafter, sometimes referred to as structural unit B). When the structure of the repeating portion of structural unit A is a structure derived from an ethylenically unsaturated compound, examples of the compound constituting structural unit B (hereinafter, sometimes referred to as compound B) include the above-mentioned hydroxyl group-containing ethylenically unsaturated compounds, carboxyl group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, and amino group-containing ethylenically unsaturated compounds. In the present disclosure, aromatic unsaturated compounds, aliphatic ethylenically unsaturated compounds, vinyl ethers; fatty acid vinyls; N-substituted maleimides; and the like can also be used as compound B. In the present disclosure, compound A preferably contains, as structural unit B, a structural unit derived from at least one compound selected from the group consisting of a hydroxyl group-containing ethylenically unsaturated compound, a carboxyl group-containing ethylenically unsaturated compound, an aliphatic ethylenically unsaturated compound, and an aromatic unsaturated compound, more preferably a structural unit derived from at least one compound selected from the group consisting of a hydroxyl group-containing ethylenically unsaturated compound, a carboxyl group-containing ethylenically unsaturated compound, and an aromatic unsaturated compound, even more preferably a structural unit derived from at least one compound selected from the group consisting of a carboxyl group-containing ethylenically unsaturated compound and an aromatic unsaturated compound, and particularly preferably a structural unit derived from an aromatic unsaturated compound. This is because the above curing agent material facilitates the formation of a curing agent with excellent low-temperature curing properties and storage stability.

[0105] Examples of the aromatic unsaturated compound include styrenes and aromatic acrylates. In the present disclosure, it is preferable that the aromatic unsaturated compound includes a styrene. This is because the curing agent material has low-temperature curing properties and storage stability, making it easy to form an excellent curing agent. Examples of the styrenes include styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, vinyltoluene, and indene. In the present disclosure, it is preferable that the styrenes include styrene or α-methylstyrene, and it is more preferable that they include styrene. This is because the curing agent material has low-temperature curing properties and storage stability, making it easy to form an excellent curing agent. Examples of the aromatic acrylates include n-propylphenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and rosin acrylate. In this specification, "(meth)acrylate" refers to either "acrylate" or "methacrylate."

[0106] Examples of the aliphatic ethylenically unsaturated compound include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2,2,4-trimethylcyclohexyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, methyl ... aliphatic acrylates such as dicyclopentenyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, tricyclo-(5,2,1,0,2.6)-decanyl(meth)acrylate, and tricyclo-(5,2,1,0,2.6)-decanyloxyethyl(meth)acrylate; and α-olefins having from 2 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 4-methyl-1-pentene, and 6-methyl-1-heptene.

[0107] Examples of the vinyl ethers include ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, etc. Examples of the fatty acid vinyls include vinyl acetate and vinyl propionate, etc. Examples of the N-substituted maleimides include N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, etc.

[0108] The content of the structural unit B is preferably 10 parts by mass or more and 90 parts by mass or less, more preferably 30 parts by mass or more and 70 parts by mass or less, even more preferably 35 parts by mass or more and 60 parts by mass or less, particularly preferably 40 parts by mass or more and 50 parts by mass or less, and most preferably 40 parts by mass or more and 48 parts by mass or less, per 100 parts by mass of compound A. This is because the above curing agent material facilitates the formation of a curing agent that is excellent in low-temperature curing property and storage stability.

[0109] The content of the structural unit B is preferably 1 mol or more and 99 mol or less, more preferably 40 mol or more and 95 mol or less, even more preferably 50 mol or more and 90 mol or less, particularly preferably 60 mol or more and 85 mol or less, and most preferably 70 mol or more and 80 mol or less, per 100 mol of all structural units contained in the compound A. This is because the curing agent material facilitates the formation of a curing agent excellent in low-temperature curing property and storage stability.

[0110] The content of the structural unit derived from an aromatic unsaturated compound in structural unit B is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, particularly preferably 95 parts by mass or more, and most preferably 98 parts by mass or more, per 100 parts by mass of structural unit B. This is because the above curing agent material facilitates the formation of a curing agent that is excellent in low-temperature curing properties and storage stability.

[0111] The content of the structural unit derived from a carboxyl group-containing ethylenically unsaturated compound in the structural unit B is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, per 100 parts by mass of the structural unit B. This is because the above curing agent material facilitates the formation of a curing agent that is excellent in low-temperature curing properties and storage stability.

[0112] (4) Compound A The amine value of Compound A may be any value that provides the desired low-temperature curing properties and storage stability, but is preferably 100 mgKOH / g or more and 500 mgKOH / g or less, more preferably 120 mgKOH / g or more and 300 mgKOH / g or less, even more preferably 150 mgKOH / g or more and 250 mgKOH / g or less, and particularly preferably 170 mgKOH / g or more and 230 mgKOH / g or less. The amine value represents the number of milligrams of KOH equivalent to the amount of HCl required to neutralize 1 g of sample. Such an amine value can be measured by a known method, for example, based on JIS K7237-1995.

[0113] 2. Uses The curing agent material may be used alone as a curing agent, but is preferably used in combination with an anionic curing agent, because this more effectively exhibits the effect of facilitating the formation of a curing agent having excellent low-temperature curing properties and storage stability.

[0114] Here, the details of the anionic curing agent can be the same as those described in the section "B. Curing Agent" below, and therefore a detailed description thereof will be omitted here. When the curing agent material is used in combination with an anionic curing agent, the content of the anionic curing agent in 100 parts by mass of the anionic curing agent and compound A can also be the same as those described in the section "B. Curing Agent" below, and therefore a detailed description thereof will be omitted here.

[0115] The curing agent material may be used in any manner as long as it can exhibit the desired curing properties, and may be used as a heat curing agent that exhibits curing properties upon heating, or as a photocuring agent that exhibits curing properties upon energy ray irradiation. In the present disclosure, the curing agent material is preferably used as a heat curing agent. This is because the curing agent material can more effectively exhibit the effect of being able to form a curing agent with excellent low-temperature curing properties and storage stability.

[0116] Applications of the curable composition using the above-mentioned curing agent material include semiconductor encapsulation materials, laminates for printed wiring boards, electronic component adhesives, electronic component encapsulants, casting materials, varnishes, paints, structural adhesives, and fiber-reinforced composite materials. In the present disclosure, the application is preferably an adhesive, more preferably an electronic component adhesive or a structural adhesive, and even more preferably a structural adhesive. Furthermore, the structural adhesive is preferably one used to join metal members and the like in a wide range of fields such as automobiles, ships, aviation, space, civil engineering, and architecture, and more preferably a structural adhesive for automobiles.

[0117] B. Curing Agent Next, the curing agent of the present disclosure will be described. The curing agent of the present disclosure is characterized by containing a compound that includes a structural unit having a tertiary amine structural group and has a weight average molecular weight of 5,000 or more and 30,000 or less, and an anionic curing agent.

[0118] The curing agent of the present disclosure has excellent low-temperature curing properties and storage stability.

[0119] The curing agent of the present disclosure contains Compound A and an anionic curing agent. Each component of the curing agent of the present disclosure will be described in detail below.

[0120] 1. Compound A The details of Compound A used in the present disclosure can be the same as those described in the above section "A. Hardener Material," and therefore, description thereof will be omitted here.

[0121] The content of compound A is preferably 5 to 90 parts by mass, more preferably 10 to 70 parts by mass, even more preferably 15 to 50 parts by mass, particularly preferably 20 to 40 parts by mass, and most preferably 25 to 35 parts by mass, per 100 parts by mass of the curing agent, because the curing agent has superior low-temperature curing properties and storage stability.

[0122] 2. Anionic Curing Agent The anionic curing agent may be any agent used for anionic curing. Such anionic curing agents may be those other than Compound A, such as acid anhydride curing agents, phenolic curing agents, amine curing agents, polythiol curing agents, etc. In the present disclosure, it is preferable that the anionic curing agent includes an amine curing agent. This is because the curing agent has superior low-temperature curing properties and storage stability. For example, those described as curing agents in International Publication No. 2022 / 168665 can be used as such anionic curing agents.

[0123] Examples of the amine-based curing agent include amines and modified amines obtained by modifying amines. The amine-based curing agent may contain at least one of the amines and modified amines, but a phenol mixture containing at least one of the amines and modified amines and a phenolic resin may also be used. That is, in the present disclosure, the amine-based curing agent may be an amine, a modified amine, or a phenol mixture. In the present disclosure, it is preferable that the amine-based curing agent contains an amine. This is because the curing agent has superior low-temperature curing properties and storage stability.

[0124] Methods for modifying amines include dehydration condensation with carboxylic acid, addition reaction with epoxy resin, addition reaction with isocyanate, Michael addition reaction, Mannich reaction, condensation reaction with urea, and condensation reaction with ketone.

[0125] (1) Amines Examples of the amines include aliphatic polyamines, aromatic polyamines, guanamines, tertiary amines, melamine, ureas, and amine compounds with a urea structure. In the present disclosure, the amines preferably include guanamines or tertiary amines, and more preferably include guanamines. This is because the curing agent has superior low-temperature curing properties and storage stability. In particular, guanamines have a high curing temperature when used alone as a curing agent, and their use in combination with the curing agent material enhances the low-temperature curing effect.

[0126] Examples of the guanamines include dicyandiamide, benzoguanamine, and acetoguanamine. In the present disclosure, the guanamines preferably include dicyandiamide, because the curing agent has superior low-temperature curing properties and storage stability.

[0127] Commercially available guanamines include Omicure DDA-5 manufactured by PTI Japan Co., Ltd., DICY7, DICY15, and DICY50 manufactured by Mitsubishi Chemical Corporation, and ADEKA Hardener EH-3636AS and ADEKA Hardener EH-4351S manufactured by ADEKA Corporation.

[0128] As the tertiary amines, compounds other than Compound A that contain a tertiary amine structural group can be used.

[0129] The tertiary amines preferably have only tertiary amine structural groups as amino groups, because the curing agent has superior low-temperature curing properties and storage stability.

[0130] The molecular weight of the tertiary amines is preferably from 50 to 2,000, more preferably from 60 to 1,000, even more preferably from 70 to 500, and particularly preferably from 80 to 300. This is because the curing agent has excellent low-temperature curing properties and storage stability.

[0131] The tertiary amine structural group possessed by the tertiary amines may have at least one of a tertiary amino group and a cyclic tertiary amino group, but preferably contains the tertiary amino group, and more preferably contains a group represented by the general formula (1), because the curing agent has better low-temperature curing properties and storage stability.

[0132] R in the general formula (1) used for the tertiary amines 1 and R 2 The preferred groups of can be the same as those described in the section "(2) Structural units having a tertiary amine structural group" in "A. Curing agent materials" above, and therefore further explanation will be omitted here.

[0133] The number of nitrogen atoms constituting the tertiary amine structural group of the tertiary amines may be 1 or more, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2. This is because the curing agent has better low-temperature curing properties and storage stability.

[0134] Examples of the compound having a tertiary amino group include compounds that do not have a cyclic tertiary amino group, such as N,N-dimethylaminoethylamine, N,N-diethylaminoethylamine, N,N-diisopropylaminoethylamine, N,N-diallylaminoethylamine, N,N-benzylmethylaminoethylamine, N,N-dibenzylaminoethylamine, N,N-cyclohexylmethylaminoethylamine, N,N-dicyclohexylaminoethylamine, N,N-dimethylaminopropylamine, and N,N-diethyl Aminopropylamine, N,N-diisopropylaminopropylamine, N,N-diallylaminopropylamine, N,N-benzylmethylaminopropylamine, N,N-dibenzylaminopropylamine, N,N-cyclohexylmethylaminopropylamine, N,N-dicyclohexylaminopropylamine, N,N-dimethylisophoronediamine, N,N-dimethylbisaminocyclohexane, N,N,N'-trimethylethylenediamine, N'-ethyl-N,N-dimethylethylenediamine, N,N,N'-trimethyl Methylethylenediamine, N'-ethyl-N,N-dimethylpropanediamine, N'-ethyl-N,N-dibenzylaminopropylamine; 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-bisaminopropylcyclohexylamine silamine, N,N-bisaminopropylbenzylamine, 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, 4-(N,N-dimethylamino)benzylamine, 4-(N,N-diethylamino)benzylamine, 4-(N,N-diisopropylamino)benzylamine, and the like.Furthermore, compound C listed in the above section "A. Curing Agent Material" can also be used as a compound having a tertiary amino group. In the present disclosure, it is preferable that the compound having a tertiary amino group is compound C. This is because it becomes a curing agent excellent in low-temperature curing properties and storage stability, and in particular, it is easy to make a curing agent excellent in low-temperature curing properties. Note that the preferred structure of compound C can be the same as that described in the above section "A. Curing Agent Material", and therefore description here will be omitted.

[0135] Examples of compounds having a cyclic tertiary amino group include imidazole compounds having an imidazole ring. Examples of compounds having a cyclic tertiary amino group but not an imidazole ring include compounds having an N-substituted morpholine ring, an N-substituted piperidine ring, an N-substituted piperazine ring, an N,N-substituted piperazine ring, or the like (sometimes referred to as compounds having other cyclic tertiary amino groups).

[0136] Examples of the imidazole compound include aliphatic imidazole compounds, aromatic imidazole compounds, etc. Examples of the aliphatic imidazole compound include compounds that do not have a heterocycle other than the imidazole ring and do not have an aromatic hydrocarbon ring, such as 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1,2-dimethylimidazole. Examples of the aromatic imidazole compound include compounds that have an aromatic hydrocarbon ring and do not have a heterocycle other than the imidazole ring, such as 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenylimidazole.

[0137] As the imidazole compound, in addition to the above-mentioned aliphatic imidazole compounds and aromatic imidazole compounds, compounds in which hydrogen atoms in the above-mentioned aliphatic imidazole compounds and aromatic imidazole compounds are substituted with substituents can also be used. For example, cyano group-containing imidazole compounds such as 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like; 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[ Triazine ring-containing imidazole compounds such as 2'-undecylimidazolyl-(1')]-ethyl-s-triazine; 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and the like can also be used.

[0138] Examples of the other compounds having a cyclic tertiary amino group include 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, and N-(3-aminopropyl)-N'-methylpiperidine.

[0139] The aliphatic polyamines may be those that do not have an aromatic hydrocarbon ring or an imidazole ring, and examples thereof include chain polyamines and alicyclic polyamines. The chain polyamines may be compounds that do not have a tertiary amine structural group and do not have an aliphatic hydrocarbon ring, and examples thereof include alkylenediamines and polyalkyleneamines. The alkylenediamines may be compounds in which two amino groups are bonded to an alkylene group, and examples thereof include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane, 1,4-diaminobutane, and hexamethylenediamine. The polyalkyleneamines may be compounds that do not have a tertiary amine structural group, have two or more amino groups, and have two or more ethylene groups (—CHCH—) bonding nitrogen atoms, and examples thereof include chain ethyleneamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, and piperazine. The alicyclic polyamines may be compounds that do not have a tertiary amine structural group but have two or more amino groups and an aliphatic hydrocarbon ring, and examples thereof include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-diaminomethylcyclohexane, 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-diaminodicyclohexylpropane, bis(4-aminocyclohexyl)sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, and norbornenediamine.

[0140] The aromatic polyamines may be compounds that do not have a tertiary amine structural group and have two or more amino groups and an aromatic hydrocarbon ring, and examples thereof include m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminebenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane.

[0141] The ureas may be those having a terminal urea group represented by the following general formula (3), and for example, compounds represented by the following general formula (31) can be used. Even if a compound has a tertiary amino group, if it has a terminal urea group it is considered to be a urea rather than a tertiary amine. Similarly, even if a compound has a primary amino group and a secondary amino group, if it has a terminal urea group it is considered to be a urea rather than an aliphatic polyamine or an aromatic polyamine.

[0142]

[0143] (In formula (3), R 201 and R 202 each independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from Group A below, * represents a bond, and Group A includes -O-, -CO-, -CO-O-, -O-CO-, -NR 11 -, -NR 11 represents CO- and -S-, and R 11 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0144]

[0145] (In formula (31), A 1 represents a monovalent organic group having 1 to 20 carbon atoms; X 1represents a group represented by the above general formula (3), and u1 represents an integer of 1 to 4. When u1 is 2 or more, a plurality of X 1 may be the same as or different from each other.)

[0146] R 201 and R 202 The hydrocarbon group having 1 to 20 carbon atoms and the substituents substituting hydrogen atoms in the hydrocarbon group used in R 1 Examples of the hydrocarbon groups and substituents used in the above are those described above.

[0147] In the present disclosure, the above R 201 and R 202 are each independently preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, even more preferably a substituted or unsubstituted hydrocarbon group having 1 to 5 carbon atoms, particularly preferably a substituted or unsubstituted hydrocarbon group having 1 to 3 carbon atoms, and most preferably a substituted or unsubstituted hydrocarbon group having 1 to 2 carbon atoms. This is because the curing agent has superior low-temperature curing properties and storage stability. In the present disclosure, 201 and R 202 is preferably an unsubstituted hydrocarbon group. 201 and R 202 The hydrocarbon group used in R is preferably an aliphatic hydrocarbon group, more preferably a chain aliphatic hydrocarbon group, and even more preferably an alkyl group. This is because the curing agent has superior low-temperature curing properties and storage stability. 201 and R 202 are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, even more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group or an ethyl group, because the above curing agent has superior low-temperature curing properties and storage stability.

[0148] A 1is a monovalent organic group having 1 to 20 carbon atoms, and for example, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms can be used. 1 A group in which u1-1 hydrogen atoms have been removed from the groups listed as the groups used in (1) can be used.

[0149] If u1 is 3, A 1 is a trivalent organic group, and as such a group, for example, groups having structures represented by general formulas (4) to (6) described in Japanese Patent No. 6650151 can also be used. 1 is a tetravalent organic group, and as such a group, for example, a group having a structure represented by general formula (7) described in Japanese Patent No. 6650151 can also be used.

[0150] A 1 The organic group used as is preferably a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, more preferably an unsubstituted hydrocarbon group having 6 to 15 carbon atoms, even more preferably an unsubstituted hydrocarbon group having 6 to 10 carbon atoms, and particularly preferably an unsubstituted hydrocarbon group having 6 to 8 carbon atoms. This is because the above curing agent has excellent low-temperature curing properties and storage stability. 1 The hydrocarbon group used in is preferably an aromatic hydrocarbon ring-containing group, more preferably a group in which u1-1 hydrogen atoms have been removed from the aromatic ring of an aryl group, and even more preferably a monocyclic structure, because the curing agent has better low-temperature curing properties and storage stability.

[0151] u1 may be 1 or more and 4 or less, preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less, and even more preferably 2. This is because the above curing agent has better low-temperature curing properties and storage stability.

[0152] The ureas that can be used include those that do not have a tertiary amine structural group, such as 3,3'-(4-methyl-1,3-phenylene)bis(1,1-dimethylurea), 2,4-toluenebisdimethylurea, 4,4-methylenediphenylenebis(N,N-dimethylurea)1,1-dimethyl,3-(4-chlorophenyl)urea, 1,1-dimethyl,3-(3,4-chlorophenyl)urea, isophoronebisdimethylurea, 1,1-dimethyl,3-phenylurea, 1,1-dimethyl,3-(4-ethoxyphenyl)urea, 1 , 1-(4-phenylene)-bis(3,3-dimethyl)urea, 1,1-dimethyl,3-(4-ethoxyphenyl)urea, 1,1-dimethyl,3-(2-hydroxyphenyl)urea, 1,1-dimethyl,3-(3-chloro-4-methylphenyl)urea, N-phenylurea, N,N-dimethylurea fluometuron, p-chlorophenyl-N,N-dimethylurea, 3,4-dichlorophenyl-N,N-dimethylurea, N-methylurea, N,N,N'-trimethylurea, N,N,N',N'-tetramethylurea, and the like.

[0153] Commercially available ureas include Dyhard UR200, UR300, UR400, UR500, UR600, and UR700 manufactured by AlzChem; U52M manufactured by Omicure; Monuron, Fenuron, Diuron, and Chlortoluron.

[0154] The urea structure amine compound is a compound having a urea structure (—NH—C(═O)—NH—) and an amino group (primary amino group, secondary amino group, or tertiary amino group), but does not have the terminal urea group. Even if a compound has a tertiary amino group, if it has a urea structure it is not considered to be a tertiary amine, but is considered to be a urea structure-containing amine compound. Similarly, even if a compound has a primary amino group and a secondary amino group, if it has a urea structure it is not considered to be an aliphatic polyamine or an aromatic polyamine, but is considered to be a urea structure-containing amine compound.

[0155] Such an amine compound having a urea structure may be one having a group represented by the following general formula (4), and for example, a compound represented by the following general formula (41) may be used.

[0156]

[0157] (In formula (4), B represents an amino group, and R 203 represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from the following Group A, * represents a bond, and Group A includes -O-, -CO-, -CO-O-, -O-CO-, -NR 11 -, -NR 11 represents CO- and -S-, and R 11 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0158]

[0159] (In formula (41), A 2 represents a divalent organic group having 1 to 20 carbon atoms; X 2 represents a group represented by the above general formula (4), and u2 represents an integer of 1 to 4. When u2 is 2 or more, a plurality of X 2 may be the same as or different from each other.)

[0160] R 203 The divalent hydrocarbon group having 1 to 20 carbon atoms used in R 1 Examples of the hydrocarbon groups used in the above R include groups in which one hydrogen atom has been removed. 203 are each independently preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, even more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a substituted or unsubstituted divalent hydrocarbon group having 2 to 4 carbon atoms. This is because the curing agent has superior low-temperature curing properties and storage stability. In the present disclosure, 203is preferably an unsubstituted hydrocarbon group. 203 The divalent hydrocarbon group used in is preferably a divalent aliphatic hydrocarbon group, more preferably a divalent chain aliphatic hydrocarbon group, and even more preferably an alkylene group, because the curing agent has superior low-temperature curing properties and storage stability. 203 are each independently preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, even more preferably an alkylene group having 2 to 4 carbon atoms, and particularly preferably an n-propylene group or an isopropylene group, because the above curing agent has superior low-temperature curing properties and storage stability.

[0161] The amino group used for B may be any of a primary amino group, a secondary amino group, and a tertiary amino group.

[0162] In the present disclosure, it is preferable that B is a primary amino group (—NH 2 ) or a tertiary amino group.

[0163] Examples of the tertiary amino group include the groups listed as the group represented by the general formula (1). The preferred structure of the tertiary amino group used in B can be the same as that described as the preferred structure of the group represented by the general formula (1).

[0164] Above A 2 is a divalent organic group having 1 to 20 carbon atoms, and for example, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms can be used. 1 The groups may be the same as those given as groups that can be used as the groups.

[0165] Above A 2The hydrocarbon group used in is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 2 to 15 carbon atoms, even more preferably a hydrocarbon group having 5 to 12 carbon atoms, and particularly preferably a hydrocarbon group having 6 to 10 carbon atoms. This is because the curing agent has superior low-temperature curing properties and storage stability. 2 The A is preferably an unsubstituted hydrocarbon group, because the curing agent has excellent low-temperature curing properties and storage stability. 2 The hydrocarbon group used in is preferably an aliphatic hydrocarbon group, more preferably an aliphatic ring-containing group, and even more preferably a group in which u2-1 hydrogen atoms have been removed from the aliphatic hydrocarbon ring of a cycloalkylalkyl group. This is because the curing agent has better low-temperature curing properties and storage stability. In the present disclosure, when u2 is 2, the curing agent in 2 is preferably a group in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring of a cycloalkylalkyl group having 1 to 20 carbon atoms, more preferably a group in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring of a cycloalkylalkyl group having 2 to 15 carbon atoms, even more preferably a group in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring of a cycloalkylalkyl group having 5 to 12 carbon atoms, and particularly preferably a group in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring of a cycloalkylalkyl group having 6 to 10 carbon atoms. This is because the above curing agent has superior low-temperature curing properties and storage stability.

[0166] u2 may be 1 or more and 4 or less, preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less, and even more preferably 2. This is because the above curing agent has better low-temperature curing properties and storage stability.

[0167] Above X 2 is a group represented by the above general formula (4), and when u2 is 2 or more, a plurality of X 2 In the present disclosure, when u2 is 2 or more, the plural X2 It is preferable that one of B is a primary amino group, that is, the urea structure amine compound is a compound having a primary amino group, and a plurality of X 2 It is preferable that one of B is a tertiary amino group, that is, the urea structure amine compound is a compound having both a primary amino group and a tertiary amino group. This is because the curing agent has better low-temperature curing properties and storage stability. Specifically, when u2 is 2, one of X 2 B is a primary amino group, and the other X 2 Preferably, B is a tertiary amino group, because the curing agent has superior low-temperature curing properties and storage stability.

[0168] The synthesis method of the urea structure amine compound is not particularly limited, but for example, it can be obtained by reacting a compound having two or more amino groups with an isocyanate compound. For example, in the above general formula (41), u2 is 2 and one of X 2 B is a primary amino group, and the other X 2 When B is a tertiary amino group, it can be obtained by reacting a compound having two primary amino groups, a compound having a primary amino group and a tertiary amino group, and a diisocyanate compound.

[0169] The isocyanate compound is not particularly limited as long as it is a compound having at least one isocyanate group in the molecule, and a monoisocyanate having one isocyanate group in the molecule or a polyisocyanate having two or more isocyanate groups in the molecule can be used.

[0170] The optional combination may be one monoisocyanate alone, two or more monoisocyanates in combination, one polyisocyanate alone, two or more polyisocyanates in combination, or a combination of a monoisocyanate and a polyisocyanate.

[0171] Examples of monoisocyanates include ethyl isocyanate, butyl isocyanate, propyl isocyanate, isopropyl isocyanate, tert-butyl isocyanate, dodecyl isocyanate, cyclohexyl isocyanate, octadecyl isocyanate, (R)-(+)-α-methylbenzyl isocyanate, (S)-(-)-α-methylbenzyl isocyanate, (R)-(-)-1-(1-naphthyl)ethyl isocyanate, ethyl isocyanatoacetate, butyl isocyanatoacetate, benzyl isocyanate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, (S)-(-)-2-methylisocyanatopropionate, methyl (S)-2-methylisocyanato-3-phenylpropionate, 2-methylisocyanatoethyl methacrylate, 3-(triethoxysilyl)propyl isocyanate, and 6,7-methylenedioxy-(4-methylisocyanatocoumarin).

[0172] Specific examples of polyisocyanates include diisocyanates such as propane-1,2-diisocyanate, 2,3-dimethylbutane-2,3-diisocyanate, 2-methylpentane-2,4-diisocyanate, octane-3,6-diisocyanate, 3,3-dinitropentane-1,5-diisocyanate, octane-1,6-diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, tolylene diisocyanate, xylylene diisocyanate, meta-tetramethylxylylene diisocyanate, isophorone diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, diphenylmethane-4,4'-diisocyanate, hydrogenated tolylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

[0173] As the compound having two or more amino groups, those having two or more amino groups among the above-mentioned tertiary amines, aliphatic polyamines, aromatic polyamines, etc. can be used. Furthermore, as the compound having two or more amino groups, two or more types may be used in combination. For example, as the compound having two or more amino groups, aliphatic polyamines and tertiary amines may be used in combination.

[0174] (2) Modified Amines Modified amines are obtained by modifying the above-mentioned amines.

[0175] Examples of amines constituting such modified amines include those compounds described in the above section "(1) Amines" that have at least one of a primary amino group and a secondary amino group. Examples of amines used in the modified amines include tertiary amines containing at least one of a primary amino group and a secondary amino group, aliphatic polyamines, aromatic polyamines, and urea-structured amine compounds containing at least one of a primary amino group and a secondary amino group. In the present disclosure, tertiary amines containing at least one of a primary amino group and a secondary amino group, and urea-structured amine compounds containing at least one of a primary amino group and a secondary amino group are preferred, and urea-structured amine compounds containing at least one of a primary amino group and a secondary amino group are more preferred. This is because the curing agent has superior low-temperature curing properties and storage stability.

[0176] The modification method used for the above-mentioned modified amines is preferably an addition reaction with an epoxy resin, i.e., an epoxy resin modified product of an amine, because the above-mentioned curing agent has better low-temperature curing properties and storage stability.

[0177] Examples of epoxy resins used in the modified amines include monoglycidyl ether compounds, monoglycidyl ester compounds, polyglycidyl ether compounds of mononuclear polyhydric phenol compounds, polyglycidyl ether compounds of polynuclear polyhydric phenol compounds or alkylene oxide adducts of the polynuclear polyhydric phenol compounds, polyglycidyl ethers of polyhydric alcohols, homopolymers or copolymers of glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids and glycidyl methacrylate, epoxy compounds having a glycidylamino group, epoxidized products of cyclic olefin compounds, epoxidized conjugated diene polymers, heterocyclic compounds, etc. More specific examples include the epoxy compounds described in the section "2. Curable Compounds" of "C. Curable Compositions" described below.

[0178] Examples of the polynuclear polyhydric phenol compound include a compound having a naphthalene structure, a compound having a biphenol structure, a compound having a bisphenol structure, and a novolac phenol resin. In the present disclosure, the polynuclear polyhydric phenol compound is preferably a compound having a bisphenol structure. This is because the curing agent has excellent low-temperature curing properties and storage stability.

[0179] Examples of compounds having a bisphenol structure include compounds in which two hydroxyphenyl groups are bonded by one atom, such as methylenebisphenol (bisphenol F), methylenebis(ortho-cresol); ethylidenebisphenol; compounds having a bisphenol A structure such as isopropylidenebisphenol (bisphenol A), isopropylidenebis(ortho-cresol), and tetrabromobisphenol A; and 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, and oxybisphenol. The phrase "two hydroxyphenyl groups bonded by one atom" refers to a linking chain length of one atom connecting the benzene rings of the two hydroxyphenyl groups. The bisphenol A structure refers to a structure in which two hydroxyphenyl groups are bonded to each other via an isopropylidene group on the benzene rings, and polyglycidyl ethers of polyhydric phenol compounds having this structure include so-called bisphenol A epoxy resins. Furthermore, examples of compounds having a bisphenol structure in which two hydroxyphenyl groups are bonded by two or more atoms include 1,3-bis(4-hydroxycumylbenzene) and 1,4-bis(4-hydroxycumylbenzene).

[0180] Examples of the alkylene oxide constituting the alkylene oxide adduct of the polynuclear polyhydric phenol compound include ethylene oxide and propylene oxide.

[0181] The content of the epoxy resin-derived moiety in the modified amines can be 10 parts by mass or more and 60 parts by mass or less, preferably 20 parts by mass or more and 50 parts by mass or less, and more preferably 25 parts by mass or more and 45 parts by mass or less, per 100 parts by mass of the modified amines, because the curing agent has superior low-temperature curing properties and storage stability.

[0182] (3) Phenol Mixture The phenol mixture contains at least one of the amines and modified amines, and a phenolic resin. In the present disclosure, the phenol mixture preferably contains a modified amine and a phenolic resin. This is because the curing agent has superior low-temperature curing properties and storage stability.

[0183] The amines constituting the modified amines used in the phenol mixture can be the same as those described in the modified amines section above, but are preferably tertiary amines containing at least one of a primary amino group and a secondary amino group, or urea-structure amine compounds containing at least one of a primary amino group and a secondary amino group, and are particularly preferably tertiary amines containing at least one of a primary amino group and a secondary amino group. This is because the curing agent has better low-temperature curing properties and storage stability. The preferred structures of the tertiary amines containing at least one of a primary amino group and a secondary amino group, and the urea-structure amine compounds containing at least one of a primary amino group and a secondary amino group can be the same as those described in the "(2) Modified Amines" section above.

[0184] The phenolic resin used in the phenol mixture may be a compound having two or more phenolic hydroxyl groups. 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 or biphenylene groups, Xylok resins), naphthol aralkyl resins, trisphenylol methane resins, and tetraphenylol ethanol. Examples of the polyhydric phenol compound include polyphenol resins, naphthol novolac resins, naphthol-phenol co-condensed novolac resins, naphthol-cresol co-condensed novolac resins, biphenyl-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked via bismethylene groups), biphenyl-modified naphthol resins (polyhydric naphthol compounds in which phenol nuclei are linked via bismethylene groups), aminotriazine-modified phenol 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 novolac resins (polyhydric phenol compounds in which phenol nuclei and alkoxy group-containing aromatic rings are linked via formaldehyde).

[0185] Examples of phenolic resins include phenol novolac H-1, H-2, H-3, H-4, H-5, and MEP-1100-N manufactured by Meiwa Kasei Co., Ltd., phenol novolac (PSM series, for example, PSM-4326) manufactured by Gun-ei Chemical Industry Co., Ltd., orthocresol novolac MER-130, triphenolmethane type MEH-7500, tetrakisphenol type MEH-7600, naphthol type MEH-7700, phenol aralkyl type MEH-7800, MEH-7851, triphenol type R-3, bisphenol novolac type MEP-6309, MEP-6309E, and liquid phenol novolac MEH-8000H, MEH-8005, MEH-8010, MEH-8015, and MEH-8205. Examples of dicyclopentadiene phenol epoxy resins include ERM-6085, ERM-6095, ERM-6105, ERM-6115, ERM-6125, and ERM-6140 manufactured by SONGWON Co., Ltd.

[0186] In the present disclosure, the linking group linking the phenols constituting the phenolic resin is preferably an alkylene group such as a methylene group or an alicyclic group such as a dicyclopentadiene group, more preferably a phenol novolac resin, a cresol novolac resin, or a dicyclopentadiene phenol adduct resin, and even more preferably a phenol novolac resin or a dicyclopentadiene phenol adduct resin, because the composition can be used as a curing agent having an excellent balance between storage stability and low-temperature curing ability.

[0187] The content of the phenolic resin in the phenol mixture is preferably 1 part by mass or more and 70 parts by mass or less, more preferably 10 parts by mass or more and 65 parts by mass or less, even more preferably 30 parts by mass or more and 60 parts by mass or less, particularly preferably 35 parts by mass or more and 55 parts by mass or less, and most preferably 40 parts by mass or more and 50 parts by mass or less, per 100 parts by mass of the mixture, because the curing agent has superior low-temperature curing properties and storage stability.

[0188] (4) Combination Product The anionic curing agent may also be a combination product in which two or more types of anionic curing agents are used in combination.

[0189] Such a combination is preferably a combination containing two or more types of amine-based curing agents, more preferably a combination containing amines, even more preferably a combination containing at least two or more types of amines (hereinafter may be referred to as combination 1), a combination containing at least amines and modified amines (hereinafter may be referred to as combination 2), and a combination containing at least an amine and a phenol mixture (hereinafter may be referred to as combination 3), with combination 1 being particularly preferred. This is because the curing agent has superior low-temperature curing properties and storage stability.

[0190] The amines contained in the combination product preferably include the guanamines, because this provides the curing agent with superior low-temperature curing properties and storage stability.

[0191] The amines contained in the combination product 1 preferably include the guanamines. This is because the curing agent has superior low-temperature curing properties and storage stability. In the present disclosure, the combination product 1 preferably includes the guanamines and at least one selected from the group consisting of ureas and tertiary amines, more preferably includes guanamines and ureas, and even more preferably includes guanamines and both ureas and tertiary amines. This is because the curing agent has superior low-temperature curing properties and storage stability.

[0192] The guanamines and amines other than guanamines that are preferably used are the same as those listed above as being preferably usable in the section "(1) Amines."

[0193] The amines contained in the above-mentioned combination products 2 and 3 preferably include the above-mentioned guanamines. This is because the above-mentioned curing agents have better low-temperature curing properties and storage stability. The above-mentioned combination products 2 and 3 preferably include the above-mentioned guanamines and tertiary amines as amines. This is because the above-mentioned curing agents have better low-temperature curing properties and storage stability. The amines, modified amines, and phenol mixtures preferably used in the above-mentioned combination products 2 and 3 can be the same as those preferably used in the above sections "(2) Modified amines" and "(3) Phenol mixtures." This is because the above-mentioned curing agents have better low-temperature curing properties and storage stability.

[0194] (5) Others The content of the anionic curing agent is preferably 10 to 95 parts by mass, more preferably 40 to 90 parts by mass, even more preferably 50 to 85 parts by mass, particularly preferably 60 to 80 parts by mass, and most preferably 65 to 75 parts by mass, per 100 parts by mass of the curing agent. This is because the curing agent has excellent low-temperature curing properties and storage stability. From the viewpoint of facilitating the formation of a cured product with excellent adhesiveness, the content of the anionic curing agent is preferably 60 to 99 parts by mass, more preferably 80 to 99 parts by mass, even more preferably 85 to 98.5 parts by mass, particularly preferably 90 to 98 parts by mass, and most preferably 94 to 97.5 parts by mass, per 100 parts by mass of the curing agent. This is because the curing agent has excellent low-temperature curing properties and storage stability. Furthermore, this is because the curing agent has excellent low-temperature curing properties and storage stability.

[0195] The content of the anionic curing agent is preferably 10 to 95 parts by mass, more preferably 40 to 90 parts by mass, even more preferably 50 to 85 parts by mass, particularly preferably 60 to 80 parts by mass, and most preferably 65 to 75 parts by mass, per 100 parts by mass of the anionic curing agent and compound A combined. This is because the curing agent has excellent low-temperature curing properties and storage stability. The content of the anionic curing agent is preferably 60 to 99 parts by mass, more preferably 85 to 98.5 parts by mass, even more preferably 90 to 98 parts by mass, particularly preferably 94 to 97.5 parts by mass, per 100 parts by mass of the anionic curing agent and compound A combined. This is because the curing agent has excellent low-temperature curing properties and storage stability.

[0196] When the anionic curing agent contains guanamines, the content of the guanamines is preferably 10 to 99 parts by mass, more preferably 50 to 95 parts by mass, even more preferably 60 to 90 parts by mass, particularly preferably 70 to 85 parts by mass, and most preferably 75 to 85 parts by mass, per 100 parts by mass of the curing agent. This is because the curing agent has superior low-temperature curing properties and storage stability. Furthermore, this is because it facilitates the formation of a cured product with excellent adhesiveness. The content of the guanamines is preferably 10 to 99 parts by mass, more preferably 50 to 95 parts by mass, even more preferably 60 to 90 parts by mass, particularly preferably 70 to 85 parts by mass, and most preferably 75 to 85 parts by mass, per 100 parts by mass of the anionic curing agent. This is because the curing agent has superior low-temperature curing properties and storage stability. Furthermore, this is because it facilitates the formation of a cured product with excellent adhesiveness. The content of the guanamines is preferably 10 parts by mass or more and 99.9 parts by mass or less, more preferably 50 parts by mass or more and 99.5 parts by mass or less, even more preferably 90 parts by mass or more and 99 parts by mass or less, particularly preferably 92 parts by mass or more and 98.5 parts by mass or less, and most preferably 95 parts by mass or more and 98 parts by mass or less, per 100 parts by mass of the total of the guanamines and compound A. This is because the curing agent has excellent low-temperature curing properties and storage stability. Furthermore, this is because it facilitates the formation of a cured product with excellent adhesiveness.

[0197] When the anionic curing agent contains a tertiary amine, the content of the tertiary amine is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 4 parts by mass or more and 15 parts by mass or less, and even more preferably 6 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the anionic curing agent. This is because the curing agent has superior low-temperature curing properties and storage stability. In addition, it is easy to lower the melting point of the curing agent, resulting in a curing agent that is particularly excellent in low-temperature curing properties and storage stability. Note that the content of tertiary amines does not include modified tertiary amines.

[0198] The content of the tertiary amines is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and preferably 0.3 to 1 part by mass, per 100 parts by mass of the curing agent in total. This is because the curing agent has superior low-temperature curing properties and storage stability. Furthermore, this facilitates the formation of a cured product with excellent adhesion. The content of the tertiary amines is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and preferably 0.3 to 1 part by mass, per 100 parts by mass of the anionic curing agent in total. This is because the curing agent has superior low-temperature curing properties and storage stability. Furthermore, this facilitates the formation of a cured product with excellent adhesion. The content of the tertiary amines is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, and preferably 15 to 30 parts by mass, per 100 parts by mass of the tertiary amines and compound A in total. This is because the above curing agent has excellent low-temperature curing properties and storage stability, and furthermore, it facilitates the formation of a cured product with excellent adhesiveness.

[0199] When the anionic curing agent contains ureas, the content of the ureas is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 10 parts by mass or more and 30 parts by mass or less, and preferably 12 parts by mass or more and 25 parts by mass or less, per 100 parts by mass of the total curing agent. This is because the curing agent has superior low-temperature curing properties and storage stability. Furthermore, this is because it facilitates the formation of a cured product with excellent adhesive properties. The content of the ureas is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 10 parts by mass or more and 30 parts by mass or less, and preferably 15 parts by mass or more and 25 parts by mass or less, per 100 parts by mass of the anionic curing agent. This is because the curing agent has superior low-temperature curing properties and storage stability. Furthermore, this is because it facilitates the formation of a cured product with excellent adhesive properties. The content of the ureas is preferably 30 parts by mass or more and 99 parts by mass or less, more preferably 50 parts by mass or more and 98 parts by mass or less, even more preferably 60 parts by mass or more and 95 parts by mass or less, particularly preferably 65 parts by mass or more and 94 parts by mass or less, and most preferably 70 parts by mass or more and 90 parts by mass or less, per 100 parts by mass of the total of the ureas and compound A. This is because the curing agent has excellent low-temperature curing properties and storage stability. Furthermore, it makes it easy to form a cured product with excellent adhesiveness.

[0200] 3. Other Components The curing agent may contain other components in addition to compound A and the anionic curing agent. Such other components may be the same as those described in the section "C. Curable Composition" below.

[0201] 4. Uses The method of using the curing agent and the use of the curable composition using the curing agent can be the same as those described in the section "2. Uses" of "A. Curing Agent Materials" above, and therefore, description thereof will be omitted here.

[0202] C. Curable Composition Next, the curable composition of the present disclosure will be described. The curable composition of the present disclosure is characterized by containing a compound that includes a structural unit having a tertiary amine structural group and has a weight average molecular weight of 5,000 to 30,000, and a curable compound.

[0203] According to the present disclosure, a curable composition having excellent low-temperature curability and storage stability can be obtained.

[0204] The curable composition of the present disclosure contains Compound A and a curable compound. Each component of the curable composition of the present disclosure will be described below.

[0205] 1. Compound A The details of Compound A used in the present disclosure can be the same as those described in the above section "A. Hardener Material," and therefore, description thereof will be omitted here.

[0206] The content of compound A is preferably from 0.5 to 30 parts by mass, more preferably from 1 to 10 parts by mass, and even more preferably from 1.5 to 5 parts by mass, per 100 parts by mass of the curable composition, because the curable composition can more effectively exhibit the effects of excellent low-temperature curability and storage stability.

[0207] The content of compound A is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 1.5 parts by mass or more and 20 parts by mass or less, even more preferably 2 parts by mass or more and 10 parts by mass or less, and particularly preferably 2.5 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the curable compound, because the curable composition can more effectively exhibit the effects of excellent low-temperature curability and storage stability.

[0208] 2. Curable Compound The curable compound may be one that can be polymerized by anionic curing. Examples of such curable compounds include cyclic compounds, linear conjugated diene monomers, vinyl aromatic monomers, polar vinyl monomers, and α-olefin monomers (ethylene, propylene, etc.). In the present disclosure, it is preferable that the curable compound contains a cyclic compound. This is because the curable composition can more effectively exhibit the effects of excellent low-temperature curability and storage stability.

[0209] Examples of the cyclic compound include an epoxy compound, a cyclic lactone, a cyclic lactam, and a cyclic siloxane. In the present disclosure, the cyclic compound preferably includes an epoxy compound. This is because the curable composition can more effectively exhibit the effects of excellent low-temperature curability and storage stability.

[0210] Examples of the epoxy compounds include polyglycidyl ethers of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; polyglycidyl ethers of dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(ortho-cresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis(ortho-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, and terpene phenols. Polyglycidyl ethers of nuclear polyhydric phenol compounds; polyglycidyl ethers of polyhydric alcohol compounds such as ethylene glycol, propylene glycol, butylene glycol, hexanediol, polyethylene glycol, polypropylene glycol, thioglycol, dicyclopentadiene dimethanol, 2,2-bis(4-hydroxycyclohexyl)propane (hydrogenated bisphenol A), glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-alkylene oxide adducts; glycidyl esters of aliphatic, aromatic, or alicyclic polybasic acids such as 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, and endomethylenetetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate;Epoxy compounds having a glycidylamino group such as N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, diglycidyl orthotoluidine, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)-2-methylaniline, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline and N,N,N',N'-tetra(2,3-epoxypropyl)-4,4-diaminodiphenylmethane; vinylcyclohexene diepoxide, cyclopentadiene diepoxide, Examples of the modified epoxy compounds include epoxidized cyclic olefin compounds such as epoxides, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers; heterocyclic compounds such as triglycidyl isocyanurate; and modified epoxy compounds obtained by modifying these compounds. Examples of the modified epoxy compounds include urethane-modified urethane-modified epoxy resins, chelate-modified epoxy resins modified with phosphoric acid (hereinafter sometimes referred to as phosphoric acid-modified epoxy resins), and rubber-modified epoxy resins modified to include a rubber component. In the present disclosure, the modified epoxy compound may be any compound that can exhibit excellent low-temperature curing properties and storage stability, but preferably includes at least one of phosphoric acid-modified epoxy resins and rubber-modified epoxy resins. This is because it is possible to obtain a compound with excellent low-temperature curing properties and easy to obtain a compound with excellent curing properties.

[0211] The phosphoric acid-modified epoxy resin is one modified with phosphoric acid, and specific examples thereof include one obtained by reacting an epoxy compound with phosphoric acid, and one obtained by reacting an epoxy compound, phosphoric acid, and polyurethane having an isocyanate group.

[0212] The rubber-modified epoxy resin includes a rubber component obtained by homopolymerizing isoprene rubber, butadiene, styrene, acrylonitrile, chloroprene, or the like, or by copolymerizing two or more of the components, and contains an epoxy group at the terminal.

[0213] The urethane-modified epoxy resin is obtained by reacting an epoxy compound having at least one hydroxyl group in the molecule with a polyurethane having a residual isocyanate group, and the polyurethane is obtained by reacting a polyhydroxy compound with a polyisocyanate compound. During the reaction, the polyisocyanate compound can be used in an excess amount relative to the polyhydroxy compound.

[0214] The epoxy compounds may be used alone or in combination of two or more. In the present disclosure, the epoxy compounds preferably include a polyglycidyl ether of a polynuclear polyhydric phenol compound, more preferably a polyglycidyl ether of a polynuclear polyhydric phenol compound having a bisphenol structure in which two hydroxyphenyl groups are bonded by one atom, and even more preferably a polyglycidyl ether of a compound having a bisphenol A structure. This is because the curable composition can more effectively exhibit the effects of excellent low-temperature curability and storage stability.

[0215] Examples of the cyclic lactones, cyclic lactams, cyclic siloxanes, etc. include the compounds described in International Publication No. 2022 / 138769. Examples of the chain conjugated diene monomers, vinyl aromatic monomers, polar vinyl monomers, etc. include the compounds described in Japanese Patent No. 6184676.

[0216] The content of the curable compound is preferably 10 parts by mass or more and 90 parts by mass or less, more preferably 30 parts by mass or more and 80 parts by mass or less, even more preferably 40 parts by mass or more and 70 parts by mass or less, and particularly preferably 50 parts by mass or more and 65 parts by mass or less, per 100 parts by mass of the curable composition, because the curable composition can more effectively exhibit the effects of excellent low-temperature curability and storage stability.

[0217] 3. Anionic Curing Agent The curable composition preferably contains an anionic curing agent in addition to Compound A and the curable compound. This is because the curable composition has superior low-temperature curing properties and storage stability. The anionic curing agent used in the present disclosure may be the same as that described in the section "B. Curing Agent" above, and therefore will not be described here.

[0218] The content of the anionic curing agent is preferably 0.5 parts by mass or more and 15 parts by mass or less, more preferably 1 part by mass or more and 10 parts by mass or less, even more preferably 3 parts by mass or more and 8 parts by mass or less, and particularly preferably 4 parts by mass or more and 6 parts by mass or less, per 100 parts by mass of the curable composition. This is because the curable composition has excellent low-temperature curing properties and storage stability. The content of the anionic curing agent is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 20 parts by mass or less, even more preferably 4 parts by mass or more and 15 parts by mass or less, and particularly preferably 5 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of the curable composition. This is because the curing agent has excellent low-temperature curing properties and storage stability. Furthermore, it is easy to form a cured product with excellent adhesion. The content of the anionic curing agent 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, relative to 100 parts by mass of the curable compound. This is because the curing agent has superior low-temperature curing properties and storage stability. Furthermore, it facilitates the formation of a cured product with excellent adhesiveness.

[0219] The content of the anionic curing agent in 100 parts by mass of the total of the anionic curing agent and compound A can be the same as that described in the section "B. Curing agent" above, and therefore, description thereof will be omitted here.

[0220] 4. Other Components The curable composition may contain other components in addition to Compound A, the curable compound, and the anionic curing agent. Examples of such other components include a blocked isocyanate, an isocyanate curing catalyst, a filler, a plasticizer, a colorant, an antioxidant, a foaming agent, a diluent, and an ultraviolet absorber. In the present disclosure, when the curable compound is an epoxy compound, it is preferable that the other components include a blocked isocyanate and a filler. This is because the curable composition has better low-temperature curability and storage stability.

[0221] (1) Blocked Isocyanate The blocked isocyanate may be a compound having a structure in which an isocyanate group has reacted with a blocking agent. Examples of such blocked isocyanates include blocked polyisocyanate compounds, which are compounds in which an isocyanate group contained in a polyisocyanate compound has reacted with a blocking agent, and blocked urethane polyisocyanate compounds, which are compounds in which an isocyanate group contained in a urethane polyisocyanate compound obtained by reacting a polyisocyanate compound with a polyol compound has reacted with a blocking agent. In the present disclosure, it is preferable that the blocked isocyanate include a blocked urethane polyisocyanate compound. This is because the curable composition has superior low-temperature curability and storage stability.

[0222] The polyisocyanate compound may be one that does not contain a urethane bond formed by the reaction of an isocyanate group with a hydroxyl group, and examples thereof include aromatic diisocyanate compounds such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; chain aliphatic diisocyanate compounds such as hexamethylene diisocyanate and lysine diisocyanate; and alicyclic structure-containing diisocyanate compounds such as cyclohexane diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. Furthermore, the polyisocyanate compound may also be an isocyanurate compound obtained by trimerizing diisocyanate compounds such as the aromatic diisocyanate compounds, the chain aliphatic diisocyanate compounds, and the alicyclic structure-containing diisocyanate compounds. In the present disclosure, the polyisocyanate compound is preferably an alicyclic structure-containing diisocyanate compound, because the curable composition has better low-temperature curability and storage stability.

[0223] In the present disclosure, a known method can be used as a method for synthesizing an isocyanurate compound by trimerizing a diisocyanate compound. Examples of such methods include the method described in WO 2021 / 106963.

[0224] As the polyol compound, a compound having two or more hydroxyl groups in the molecule can be used, for example, polyether polyol, polyester polyol, polycarbonate polyol, polyesteramide polyol, acrylic polyol, polyurethane polyol, etc. The polyol compound may contain only one type of compound, or may contain two or more types of compounds. Such polyol compounds can be similar to those described in, for example, Japanese Patent No. 5322912, International Publication No. 2021 / 106963, etc.

[0225] Examples of the blocking agent include active methylene compounds such as malonic acid diesters (diethyl malonate, etc.), acetylacetone, and acetoacetic acid esters (ethyl acetoacetate, etc.); oxime compounds such as acetoxime, methyl ethyl ketoxime (MEK oxime), and methyl isobutyl ketoxime (MIBK oxime); monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, heptyl alcohol, hexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, isononyl alcohol, and stearyl alcohol, or isomers thereof; methyl glycol, ethyl glycol, and ethyl diglycol. glycol derivatives such as ethyl triglycol, butyl glycol, and butyl diglycol; amine compounds such as dicyclohexylamine; monophenols such as phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, and bromophenol; phenols such as resorcinol, catechol, hydroquinone, bisphenol A, bisphenol S, bisphenol F, and naphthol; and ε-caprolactone and ε-caprolactam.

[0226] Known reaction methods can be used as a method of reacting an isocyanate group contained in the polyisocyanate with a blocking agent, a method of reacting an isocyanate group contained in the polyurethane polyisocyanate with a blocking agent, etc. In the above reaction, the amount of blocking agent added, the reaction temperature, etc. can be the same as those described in Japanese Patent No. 5322912, WO 2021 / 106963, etc.

[0227] The content of the blocked isocyanate is preferably from 1 to 30 parts by mass, more preferably from 5 to 25 parts by mass, and even more preferably from 10 to 20 parts by mass, per 100 parts by mass of the curable composition, because the curable composition has better low-temperature curability and storage stability.

[0228] The content of the blocked isocyanate is preferably from 10 to 40 parts by mass, more preferably from 15 to 35 parts by mass, and even more preferably from 20 to 30 parts by mass, relative to 100 parts by mass of the curable compound, because the curable composition has better low-temperature curability and storage stability.

[0229] (2) Isocyanate Curing Catalyst The curable composition of the present disclosure preferably contains an isocyanate curing catalyst that promotes the reaction between an isocyanate group generated by elimination of a blocking agent from the blocked isocyanate and an active hydrogen group, because the curable composition has better low-temperature curability and storage stability.

[0230] Examples of the active hydrogen group include a hydroxyl group, a phenol group, an amino group, an imino group, a carboxyl group, a urethane group, a thiol group, and a sulfonic acid group.

[0231] Examples of the isocyanate curing catalyst include amine catalysts, organometallic catalysts, etc. The isocyanate curing catalyst may contain only one type, or may contain two or more types in combination.

[0232] Examples of organometallic catalysts include stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, and cobalt naphthenate. In the present disclosure, the organometallic catalyst preferably contains a tin-containing compound such as dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, or dioctyltin dilaurate, and more preferably contains dibutyltin dilaurate, dioctyltin dilaurate, or the like. This is because the curable composition has superior low-temperature curability and storage stability.

[0233] As the amine catalyst, for example, those described as catalysts used in synthesizing polyurethane resins in Japanese Patent No. 6806488 can be used.

[0234] (3) Filler When the curable composition is used to form a cured product having excellent physical strength, it preferably contains a filler. Examples of fillers include silicas such as fused silica, fused spherical silica, crystalline silica, colloidal silica, fumed silica, and silica gel; metal oxides such as alumina, iron oxide, and antimony trioxide; ceramics such as silicon nitride, aluminum nitride, boron nitride, and silicon carbide; minerals such as mica and montmorillonite; metal hydroxides such as aluminum hydroxide and magnesium hydroxide, or those modified by organic modification treatment or the like; metal carbonates such as calcium carbonate, calcium silicate, magnesium carbonate, and barium carbonate, or those modified by organic modification treatment or the like; pigments such as metal borates and carbon black; inorganic fillers such as carbon fiber, graphite, whiskers, kaolin, talc, glass fiber, glass beads, glass microspheres, silica glass, layered clay minerals, clay, silicon carbide, quartz, aluminum, and zinc; and organic fillers such as acrylic beads, polymer fine particles, transparent resin beads, wood flour, pulp, and cotton chips. In the present disclosure, the filler preferably includes an inorganic filler, more preferably includes silicas and metal carbonates, and even more preferably includes both silicas and metal carbonates.

[0235] The content of the filler is preferably from 5 to 40 parts by mass, more preferably from 10 to 30 parts by mass, and more preferably from 15 to 25 parts by mass, per 100 parts by mass of the curable composition, because the curable composition can easily form a cured product having excellent physical strength.

[0236] (4) Plasticizer Examples of the plasticizer include benzoate esters such as diethylene glycol dibenzoate; phthalate esters such as dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), and ditridecyl phthalate (DTDP); terephthalate esters such as bis(2-ethylhexyl) terephthalate (DOTP); isophthalate esters such as bis(2-ethylhexyl) isophthalate (DOIP); pyromellitic acid esters such as tetra-2-ethylhexyl pyromellitic acid (TOPM); di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl sebacate (DOS), and sebacic acid esters. phosphates such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP); alkyl esters of polyhydric alcohols such as pentaerythritol; polyesters having a molecular weight of 800 to 4,000 synthesized by polyesterification of a dibasic acid such as adipic acid with a glycol; epoxidized esters such as epoxidized soybean oil and epoxidized linseed oil; alicyclic dibasic acids such as diisononyl hexahydrophthalate; fatty acid glycol esters such as 1,4-butanediol dicaprate; acetyl tributyl citrate (ATBC); chlorinated paraffins obtained by chlorinating paraffin wax or n-paraffin; chlorinated fatty acid esters such as chlorinated stearic acid ester; and higher fatty acid esters such as butyl oleate.

[0237] (5) Colorant As the colorant, for example, inorganic pigments such as titanium dioxide and carbon black, and organic pigments such as azo pigments and phthalocyanine pigments can be used.

[0238] (6) Antioxidant As the antioxidant, for example, phenol-based or amine-based antioxidants can be used.

[0239] (7) Foaming Agent As the foaming agent, for example, azo-based foaming agents that generate gas when heated, such as azodicarbonamide and azobisformamide, can be used.

[0240] (8) Diluent As the diluent, for example, a solvent such as xylene or mineral turpentine can be used.

[0241] (9) Ultraviolet Absorber As the ultraviolet absorber, for example, a benzotriazole-based compound can be used.

[0242] The content of the other components other than the blocked isocyanate and the filler may be any content that enables the curable composition to form a desired cured product. For example, the total content of the other components other than the blocked isocyanate and the filler can be 40 parts by mass or less in 100 parts by mass of the curable composition.

[0243] The use of the curable composition is not particularly limited as long as it is an application requiring low-temperature curing property and storage stability. Such applications can be similar to those described in the section "2. Use" of "A. Curing Agent Material" above, and therefore a description thereof will be omitted here.

[0244] D. Cured Product Next, the cured product of the present disclosure will be described. The cured product of the present disclosure is characterized by being a cured product of the above-described curable composition.

[0245] According to the present disclosure, by using the above-described curable composition, it is possible to provide a cured product that is easy to form. More specifically, due to the excellent low-temperature curing property, it is possible to produce a cured product at a low temperature. Furthermore, due to the excellent storage stability, it is easy to obtain a cured product at a desired timing.

[0246] The details of the curable composition can be the same as those described in the above section "C. Curable Composition," and therefore further description will be omitted here. The method for producing the cured product may be any method capable of forming a cured product in a desired cured state, and for example, the method described in the below-described section "E. Method for Producing a Cured Product" can be used. The uses of the cured product of the present disclosure can be, for example, the same as those described as uses of the curable composition in the above section "2. Uses" of "A. Curing Agent Material."

[0247] E. Method for Producing the Cured Product Next, a method for producing the cured product of the present disclosure will be described. The method for producing the cured product of the present disclosure is characterized by having a step of heating the curable composition described above.

[0248] According to the present disclosure, by using the above-described curable composition, it is possible to provide a method for producing the cured product, which allows the cured product to be easily formed.

[0249] The method for producing a cured product according to the present disclosure includes a step of heating a curable composition. Each step of the method for producing a cured product according to the present disclosure will be described below.

[0250] 1. Heating Step This step is a step of heating the curable composition. The content of the curable composition can be the same as that described in the section "C. Curable composition" above, and therefore, description thereof will be omitted here.

[0251] The heating temperature of the curable composition may be any temperature that allows a desired cured product to be formed, and is, for example, preferably 70°C or higher and 200°C or lower, more preferably 80°C or higher and 190°C or lower, even more preferably 90°C or higher and 150°C or lower, and particularly preferably 95°C or higher and 130°C or lower, because the effects of the present disclosure can be more effectively exhibited at such a temperature.

[0252] 2. Others The method for producing a cured product according to the present disclosure includes the heating step described above, but may also include other steps as necessary. Examples of such other steps include a coating step of coating the curable composition. The uses of the cured product produced by the method for producing a cured product according to the present disclosure can be, for example, the same as those described above for the uses of the curable composition in the section "2. Uses" of "A. Curing Agent Materials."

[0253] F. Manufacturing Method of Curing Agent Material Next, a manufacturing method of the curing agent material of the present disclosure will be described. The manufacturing method of the curing agent material of the present disclosure is characterized by comprising a reaction step of reacting a polymer having a weight average molecular weight of 3,000 or more and 25,000 or less, which has a bonding functional group b that is at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, and an amino group, with a compound having a bonding functional group c that can react with the bonding functional group b to form a covalent bond and a tertiary amine structural group.

[0254] According to the present disclosure, the above-mentioned hardener material can be easily produced.

[0255] The production method of the present disclosure includes the above reaction steps. Each step of the production method of the present disclosure will be described in detail below.

[0256] 1. Reaction Step This step involves reacting a polymer (hereinafter sometimes referred to as polymer 1) having a bonding functional group b, which is at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, and an amino group, and having a weight-average molecular weight of 3,000 or more and 25,000 or less, with a compound (hereinafter sometimes referred to as compound C) having a bonding functional group c capable of reacting with the bonding functional group b to form a covalent bond and a tertiary amine structural group.

[0257] (1) Polymer 1 The polymer 1 has the binding functional group b. The details of the binding functional group b can be the same as those described in the section "A. Curing Agent Materials" above. Therefore, the carboxyl group as the binding functional group b conceptually includes a dicarboxylic acid anhydride structure. The polymer 1 can have a structural unit derived from a hydroxyl group-containing ethylenically unsaturated compound, a carboxyl group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, or an amino group-containing ethylenically unsaturated compound (hereinafter, sometimes referred to as structural unit A'). The details of the hydroxyl group-containing ethylenically unsaturated compound, carboxyl group-containing ethylenically unsaturated compound, epoxy group-containing ethylenically unsaturated compound, and amino group-containing ethylenically unsaturated compound used to form the structural unit A' can be the same as those described for compound B in the section "A. Curing Agent Materials" above. In this step, the polymer 1 preferably has, as the structural unit A', a structural unit derived from a carboxyl group-containing ethylenically unsaturated compound, more preferably a structural unit derived from an unsaturated dicarboxylic acid or an unsaturated dicarboxylic acid anhydride, even more preferably a structural unit derived from an unsaturated dicarboxylic acid anhydride, and particularly preferably a structural unit derived from maleic anhydride. This is because the production of the above-mentioned curing agent material becomes easier. Furthermore, the curing agent material produced by the production method of the present disclosure facilitates the formation of a curing agent with excellent low-temperature curing properties and storage stability.

[0258] The content of the structural unit A' is preferably 5 to 80 moles, more preferably 10 to 60 moles, and even more preferably 15 to 40 moles, per 100 moles of all structural units constituting the polymer 1. This is because this makes it easier to produce the curing agent material.

[0259] The content of the structural unit A' is preferably 5 parts by mass or more and 80 parts by mass or less, more preferably 10 parts by mass or more and 60 parts by mass or less, and even more preferably 15 parts by mass or more and 40 parts by mass or less, per 100 parts by mass of the polymer 1. This is because the production of the curing agent material described above becomes easier.

[0260] The polymer 1 can have a structural unit other than the structural unit A' (hereinafter, sometimes referred to as structural unit B'). Examples of such structural unit B' include structural units derived from aromatic unsaturated compounds, aliphatic ethylenically unsaturated compounds, vinyl ethers, fatty acid vinyls, N-substituted maleimides, etc. The details of the aromatic unsaturated compounds, aliphatic ethylenically unsaturated compounds, vinyl ethers, fatty acid vinyls, and N-substituted maleimides can be the same as those described in the section "A. Curing Agent Material" above.

[0261] The structural unit B' preferably contains a structural unit derived from at least one compound selected from the group consisting of an aliphatic ethylenically unsaturated compound and an aromatic unsaturated compound, more preferably contains a structural unit derived from an aromatic unsaturated compound, even more preferably contains a structural unit derived from a styrene, particularly preferably contains a structural unit derived from styrene or α-methylstyrene, and most preferably contains a structural unit derived from styrene. This is because the production of the above-mentioned curing agent material becomes easier. Furthermore, the curing agent material produced by the production method of the present disclosure facilitates the formation of a curing agent with excellent low-temperature curing properties and storage stability.

[0262] The content of the structural unit derived from the aromatic unsaturated compound is preferably 50 parts by mass or more, more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, particularly preferably 95 parts by mass or more, and most preferably 98 parts by mass or more, per 100 parts by mass of the structural unit B', because this makes it easier to produce the curing agent material.

[0263] The content of the structural unit B' is preferably 20 to 95 mol, more preferably 40 to 90 mol, and even more preferably 60 to 85 mol, per 100 mol of all structural units constituting the polymer 1. This is because this makes it easier to produce the curing agent material.

[0264] The content of the structural unit B' is preferably 20 parts by mass or more and 95 parts by mass or less, more preferably 40 parts by mass or more and 90 parts by mass or less, and even more preferably 60 parts by mass or more and 85 parts by mass or less, per 100 parts by mass of the polymer 1. This is because the production of the curing agent material described above becomes easier.

[0265] The weight average molecular weight of the polymer 1 is preferably 3,000 or more and 25,000 or less, more preferably 4,000 or more and 20,000 or less, even more preferably 6,000 or more and 15,000 or less, and particularly preferably 8,000 or more and 12,000 or less, because this makes it easier to produce the curing agent material.

[0266] (2) Compound C Compound C can be the same as that described in the section "A. Hardener Material" above, and therefore a description thereof will be omitted here.

[0267] The amount of compound C added may be any amount that allows the amount of compound C bound to polymer 1, i.e., the reaction amount, to be in the desired range, and is, for example, preferably 30 parts by mass or more and 300 parts by mass or less, more preferably 40 parts by mass or more and 200 parts by mass or less, even more preferably 45 parts by mass or more and 100 parts by mass or less, and particularly preferably 50 parts by mass or more and 80 parts by mass or less, relative to 100 parts by mass of polymer 1. This is because the production of the curing agent material described above becomes easier.

[0268] The amount of compound C added may be any amount that allows the amount of compound C bound to polymer 1, i.e., the reaction amount, to be in the desired range, and is, for example, preferably 0.5 mol to 5 mol, more preferably 0.6 mol to 3 mol, even more preferably 0.8 mol to 2 mol, and particularly preferably 0.85 mol to 1.4 mol, relative to 1 mol of structural unit B' contained in polymer 1. This is because this makes it easier to produce the curing agent material.

[0269] The reaction amount of the compound C, i.e., the amount of compound C bound to polymer 1, is preferably 10 parts by mass or more and 200 parts by mass or less, more preferably 20 parts by mass or more and 150 parts by mass or less, even more preferably 30 parts by mass or more and 100 parts by mass or less, and particularly preferably 45 parts by mass or more and 80 parts by mass or less, relative to 100 parts by mass of polymer 1. This is because the production of the curing agent material described above becomes easier.

[0270] The reaction amount of the compound C, that is, the amount of compound C bound to polymer 1, is preferably 0.1 mol or more and 2 mol or less, more preferably 0.2 mol or more and 1.5 mol or less, and even more preferably 0.3 mol or more and 1.0 mol or less, relative to 1 mol of structural unit B' contained in polymer 1. This is because this makes it easier to produce the curing agent material.

[0271] (3) Reaction Method The reaction method between the polymer 1 and the compound C may be any method that can form a covalent bond between the bonding functional group b of the polymer 1 and the bonding functional group c of the compound C. An example of such a reaction method is a method in which the polymer 1 and the compound C are mixed and heated. The heating temperature is preferably 0°C or higher and 200°C or lower, more preferably 50°C or higher and 150°C or lower, and even more preferably 80°C or higher and 130°C or lower. This is because the production of the curing agent material described above becomes easier.

[0272] The heating method may be a method in which the polymer 1 and compound C are heated in a solvent. Examples of the solvent include hydrocarbon solvents, ketone solvents, ether solvents, glyme solvents, and halogenated solvents. In this step, the solvent is preferably a hydrocarbon solvent, as this makes it easier to produce the curing agent material.

[0273] Examples of hydrocarbon solvents include toluene, xylene, hexane, cyclohexane, and n-heptane. In this step, the hydrocarbon solvent is preferably an aromatic hydrocarbon solvent such as toluene or xylene, and toluene is more preferred. This is because it makes it easier to produce the curing agent material. Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of ether solvents include tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane. Examples of glyme solvents include monoglyme and diglyme. Examples of halogen-based solvents include dichloromethane and chloroform.

[0274] The heating time is preferably from 0.1 to 10 hours, more preferably from 0.5 to 8 hours, and even more preferably from 1 to 6 hours, because this makes it easier to produce the curing agent material.

[0275] 2. Other Steps The above production method may include other steps in addition to the reaction step. Such other steps include a solvent removal step for removing the solvent, a purification step for removing unreacted materials, etc.

[0276] As a method for removing the solvent, known methods such as a method of subjecting the mixture after the reaction step to a heat treatment or a vacuum treatment can be used. As the purification step, known methods such as a washing step using a solvent or a water washing treatment, or a reprecipitation purification method can be used.

[0277] The hardener material obtained by the above-mentioned production method and its uses can be the same as those described in the above section "A. Hardener material," and therefore, description thereof will be omitted here.

[0278] G. Others The present disclosure includes the following aspects. [1] A curing agent material comprising a compound having a structural unit with a tertiary amine structural group and having a weight-average molecular weight of 5,000 or more and 30,000 or less. [2] The curing agent material according to [1], which is for use in combination with an anionic curing agent. [3] The curing agent material according to [1] or [2], wherein the tertiary amine structural group has a tertiary amino group. [4] The curing agent material according to any one of [1] to [3], wherein the structural unit having a tertiary amine structural group has at least one of a hydroxyl group and a carboxyl group. [5] The curing agent material according to any one of [1] to [4], wherein the structural unit having a tertiary amine structural group has a structural unit represented by the following general formula (100): (In the formula, R 101 and R 102 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from Group B below; 1 is -O-, -CO-, -CO-O-, -O-CO-, -CO-NR 103 - and -NR 103 represents a divalent group selected from —CO—; 103 represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from the following group B; 2 represents a (c+1)-valent hydrocarbon group having 1 to 20 carbon atoms or a group in which a methylene group in the hydrocarbon group has been substituted with a divalent group selected from the following group B, 1represents a tertiary amine structural group, Group B represents -O-, -CO-, -CO-O-, -O-CO-, -NH-, -NHCO-, and -S-, a represents an integer of 0 or 1, b represents an integer of 0 or 1, and c represents an integer of 1 to 10. [6] The curing agent material according to any of [1] to [5], wherein the content of the structural unit having the tertiary amine structural group is 1 part by mass or more and 99 parts by mass or less per 100 parts by mass of the compound. [7] The curing agent material according to any of [1] to [6], wherein the content of the structural unit having the tertiary amine structural group is 1 mole or more and 99 moles or less per 100 moles of all structural units contained in the compound. [8] The curing agent material according to any one of [1] to [7], wherein the compound contains, as a structural unit other than the structural unit having a tertiary amine structural group, a structural unit derived from at least one compound selected from the group consisting of a hydroxyl group-containing ethylenically unsaturated compound, a carboxyl group-containing ethylenically unsaturated compound, and an aromatic unsaturated compound. [9] The curing agent material according to [8], wherein the content of the structural units other than the structural unit having a tertiary amine structural group is 10 parts by mass or more and 90 parts by mass or less per 100 parts by mass of the compound.

[10] A curing agent comprising a compound including a structural unit having a tertiary amine structural group and having a weight-average molecular weight of 5,000 to 30,000, and an anionic curing agent.

[11] The curing agent according to

[10] , wherein the anionic curing agent contains an amine-based curing agent.

[12] The curing agent according to

[11] , wherein the amine-based curing agent contains a guanamine.

[13] The curing agent according to

[12] , characterized in that the content of the guanamines is 10 parts by mass or more and 99 parts by mass or less per 100 parts by mass of the anionic curing agent.

[14] The curing agent according to any one of

[11] to

[13] , characterized in that the anionic curing agent is a combination product containing two or more types of amine-based curing agents.

[15] The curing agent according to

[14] , wherein the combination is a combination containing at least two or more types of amines, a combination containing at least amines and modified amines, or a combination containing at least amines and a phenol mixture.

[16] The curing agent according to

[15] , wherein the combination containing at least two or more types of amines contains guanamines and at least one selected from the group consisting of ureas and tertiary amines.

[17] The curing agent according to

[15] , wherein the combination containing at least amines and modified amines contains, as the amines, guanamines and tertiary amines.

[18] The curing agent according to

[16] or

[17] , wherein the content of the tertiary amines is 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the total curing agent.

[19] The curing agent according to any one of

[10] to

[18] , wherein the content of the compound is 5 parts by mass or more and 90 parts by mass or less per 100 parts by mass of the curing agent.

[20] The curing agent according to any one of

[10] to

[19] , wherein the content of the anionic curing agent is 10 parts by mass or more and 95 parts by mass or less per 100 parts by mass of the total of the anionic curing agent and the compound.

[21] A curable composition comprising a compound having a structural unit with a tertiary amine structural group and having a weight average molecular weight of 5,000 to 30,000, and a curable compound.

[22] The curable composition according to

[21] , wherein the compound contains an anionic curing agent.

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

[21] or

[22] .

[24] A method for producing a cured product, comprising a step of heating the curable composition according to

[21] or

[22] .

[25] A method for producing a curing agent material, comprising a reaction step of reacting a polymer having a weight average molecular weight of 3,000 or more and 25,000 or less, the polymer having a bonding functional group b which is at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, and an amino group, with a compound having a bonding functional group c capable of reacting with the bonding functional group b to form a covalent bond and a tertiary amine structural group.

[26] The method for producing a curing agent material according to

[25] , wherein the polymer has a structural unit derived from an unsaturated dicarboxylic acid or an unsaturated dicarboxylic acid anhydride as the structural unit having the bonding functional group b.

[0279] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any configuration that is substantially identical to the technical idea described in the claims and that provides similar effects is included within the technical scope of the present disclosure.

[0280] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0281] The following materials were used for each component. (Compound B or polymer 1 having structural units derived from compound B) B1: styrene-maleic anhydride copolymer (Xiran 3000 manufactured by Polyscope; structural units derived from styrene: structural units derived from maleic anhydride = 3:1 (molar ratio), weight-average molecular weight 10,000) B2: styrene-maleic anhydride copolymer (Xiran 1000 manufactured by Polyscope; structural units derived from styrene: structural units derived from maleic anhydride = 1:1 (molar ratio), weight-average molecular weight 5,000) B3: succinic anhydride (molecular weight 100.07)

[0282] (Compound C) C1: A compound represented by the following formula (C1) (ADEKA Hardener EHC-30, manufactured by ADEKA Corporation)

[0283]

[0284] Example 1 A curing agent material containing Compound A1 was produced by reacting the components according to the formulation shown in Table 1 below, using the following procedure. 100 parts by mass of Compound B1 and 45 parts by mass of Compound C1 were added to 120 parts by mass of toluene solvent, and the mixture was allowed to react at 110°C for 3 hours while stirring. The solvent was distilled off at 110°C, and the mixture was finally heated to 140-160°C under reduced pressure of 40 hPa or less and dried by heating to obtain Compound A1 containing a structural unit having a tertiary amine structural group. The upper value in the Compound C1 column in Table 1 represents the amount (parts by mass) of Compound C1 relative to 100 parts by mass of Compound B1, and the lower value represents the molar ratio of Compound C1 relative to 1 mole of the structural unit derived from maleic anhydride in Compound B1. The weight-average molecular weight and amine value of the resulting Compound A1 were measured under the following conditions. The measurement results are shown in Table 1.

[0285] (Weight-average molecular weight) GPC: HLC-8320GPC (manufactured by Tosoh Corporation) Solvent: DMF (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) / 10 mM LiBr solution Flow rate: 0.6 mL / min Column: TSKgel guard column Super AW-H (4.6 mm I.D. × 3.5 cm) × 1 + TSKgel Super AWM-H (6.0 mm I.D. × 15 cm) × 2 (manufactured by Tosoh Corporation) As column pretreatment, a DMF / 100 mM triethylamine solution was passed through the column before measurement to mask the adsorption points in advance. Column temperature: 40°C Sample concentration: 1 mg / mL Injection volume: 20 μL Polystyrene standards for calibration curve: Mw 5,480,000, 1,090,000, 427,000, 96,400, 37,900, 10,200, 2,550, 598 (manufactured by Tosoh)

[0286] (Amine Value) The amine value was measured in accordance with JIS K7237-1995.

[0287] [Examples 2 to 4] In the same manner as in Example 1, compounds A2 to A4 were obtained, each containing a structural unit having a tertiary amine structural group, in the formulations shown in Examples 2 to 4 in Table 1 below. The upper value in the column for compound C1 in Table 1 represents the amount (parts by mass) of compound C1 blended relative to 100 parts by mass of compound B1 or compound B2, and the lower value represents the molar ratio of compound C1 relative to 1 mole of the structural unit derived from maleic anhydride in compound B1 or compound B2. The measurement results for the weight-average molecular weights and amine values ​​of the resulting compounds A2 to A4 are shown in Table 1. Note that, for Example 3, a mixture of compound A3 and unreacted compound C1 was used as the sample, and the measurement result for the amine value of the entire sample is shown.

[0288] Comparative Example 1 100 parts by mass of compound B3 and 270 parts by mass of compound C1 were charged into 100 parts by mass of toluene solvent and reacted at room temperature (25°C) for 0.5 hours while stirring. After the reaction, the temperature was raised to 100°C, and the solvent was removed under reduced pressure to obtain compound A'1. Note that in Comparative Example 1, the upper value in the column for compound C1 in Table 1 represents the amount (parts by mass) of compound C1 blended relative to 100 parts by mass of compound B3, and the lower value represents the molar ratio of compound C1 to 1 mole of succinic anhydride in compound B3. The measurement results of the weight-average molecular weight of the obtained compound A'1 are shown in Table 1. Note that the amine value of compound A'1 obtained in Comparative Example 1 was determined by calculation from the theoretical amine value.

[0289]

[0290] [Examples 11 to 21 and Comparative Examples 11 to 15] Curing agents were prepared according to the formulations shown in Tables 2 and 3 below. The numerical values ​​in the columns for curing agent material and anionic curing agent in Tables 2 and 3 represent the blending amounts (parts by mass). The curing agent material and anionic curing agents used were as follows:

[0291] (Curing agent materials) A1 to A4: Compounds A1 to A4 produced in Examples 1 to 4 A'1: Compound A'1 produced in Comparative Example 1 B1: Xiran 3000 B2: Xiran 1000

[0292] (Anionic curing agent) C1: Compound represented by the above formula (C1) (ADEKA Hardener EHC-30 manufactured by ADEKA Corporation) C2: Compound represented by the following formula (C2) (Kao Corporation Kaolizer No. 25) C3: Dicyandiamide: ADEKA Hardener EH-3636AS manufactured by ADEKA Corporation

[0293]

[0294] [Evaluation] The storage stability and low-temperature curing properties of each of the obtained curing agents were evaluated according to the following procedures. The results are shown in Tables 2 and 3.

[0295] 1. Storage Stability The curing agents obtained in Examples 11 to 21 and Comparative Examples 11 to 15 were blended according to the formulations described below to obtain compositions for evaluation. The numerical values ​​in the formulations below represent parts by mass.

[0296] <Composition for evaluation> Curing agent: 10 parts by mass Epoxy compound 1: 60 parts by mass Phosphoric acid-modified epoxy resin: 10 parts by mass Rubber-modified epoxy resin: 10 parts by mass Block urethane: 20 parts by mass Filler: 25 parts by mass Filler (thixotropic agent): 1 part by mass

[0297] The following materials were used as the components of the evaluation composition. Epoxy compound 1: ADEKA RESIN EP-4100E (bisphenol A type epoxy resin, epoxy equivalent 190 g / eq) manufactured by ADEKA Corporation. Phosphate-modified epoxy resin: ADEKA RESIN EP-49-10P2 (phosphate-modified epoxy resin, epoxy equivalent 300 g / eq) manufactured by ADEKA Corporation. Rubber-modified epoxy resin: ADEKA RESIN EPR-1630 (rubber-modified epoxy resin, epoxy equivalent 900 g / eq) manufactured by ADEKA Corporation. Block urethane: ADEKA RESIN QR-9466 (blocked IPDI-based urethane polyisocyanate compound, blocked isocyanate equivalent 1400 g / eq) manufactured by ADEKA Corporation. Filler: WHITEN SB (calcium carbonate) manufactured by Shiraishi Kogyo Co., Ltd. Filler (thixotropic agent): RY-200S (fumed silica) manufactured by Nippon Aerosil Co., Ltd.

[0298] <Evaluation Method> The above evaluation compositions were left to stand in an oven at 40°C, and those that lost fluidity and gelled in less than 30 days were rated as x, those that maintained fluidity (did not gel) but showed a significant increase in viscosity were rated as △, and those that maintained their fluidity for 30 days or more were rated as ◯. Gelling was judged by palpation with a needle-shaped object, and gelation was judged to have occurred when the initial fluidity was lost and the needle-shaped object could not be placed in the composition and fell over, or when the composition was completely solidified and could not be placed upright.

[0299] 2. Low-temperature curing property Using the composition for evaluation described in the above section "1. Storage stability," the composition was applied to a frame having a size of 1 cm square and a thickness of 0.2 mm (200 μm), and the composition was heat-cured for 30 minutes in an oven at 120° C. The obtained cured product had a peak of 916 cm attributed to the epoxy group. -1 The intensity was measured using a Fourier transform infrared spectrophotometer (FT-IR), and the curing rate (%) was calculated assuming the intensity before curing as 100, and the evaluation was carried out according to the following criteria: Curing rate = peak intensity after curing x 100 / peak intensity before curing

[0300] [Evaluation criteria] ◎: 95% or more 〇: 90% or more but less than 95% △: 85% or more but less than 90% ×: Less than 85%

[0301]

[0302]

[0303] [Examples 31 to 52 and Comparative Examples 31 to 40] Curing agents were prepared according to the formulations shown in Tables 4 to 6 below. The numerical values ​​in the columns for curing agent material and anionic curing agent in Tables 4 to 6 represent the blending amounts (parts by mass). The curing agent material and anionic curing agents used were as follows:

[0304] (Curing agent material) A2: Compound A2 prepared in Example 2

[0305] (Anionic curing agents) C1: Compound represented by the above formula (C1) (ADEKA Hardener EHC-30 manufactured by ADEKA Corporation) C3: Dicyandiamide: ADEKA Hardener EH-3636AS manufactured by ADEKA Corporation C4: Compound represented by the following formula (C4) (UR300 manufactured by Alzchem Group) C5: Compound represented by the following formula (C5) (UR500 manufactured by Alzchem Group) C6: Compound represented by the following formula (C6) (UR200 manufactured by Alzchem Group) C7: Phenol mixture containing an epoxy resin-modified product of tertiary amines containing at least one of a primary amino group and a secondary amino group (EH-5046S manufactured by ADEKA Corporation) C8: Modified amines containing an epoxy resin modified product of a urea structure amine compound containing at least one of a primary amino group and a secondary amino group (EH-4370S manufactured by ADEKA Corporation); C9: Modified amines containing an epoxy resin modified product of a urea structure amine compound containing at least one of a primary amino group and a secondary amino group (EH-4360S manufactured by ADEKA Corporation); C10: Phenol mixture containing an epoxy resin modified product of aliphatic polyamines (EH-5030S manufactured by ADEKA Corporation); C11: Phenol mixture containing an epoxy resin modified product of aliphatic polyamines (EH-4358S manufactured by ADEKA Corporation).

[0306]

[0307] 3. Storage Stability 2 The curing agents obtained in Examples 31 to 52 and Comparative Examples 31 to 40 were blended according to the formulation described below to obtain evaluation compositions. The numerical values ​​for the formulations below represent parts by mass. Note that, for Example 31, the "parts by mass listed in Tables 4 to 6" described as the blending amount of curing agent in the evaluation composition means, for example, that 1.66 parts by mass of A2, 0.34 parts by mass of C1, and 7 parts by mass of C3 were blended relative to 60 parts by mass of Epoxy Compound 1. The components used in the evaluation composition were the same as those described in "1. Storage Stability." The obtained evaluation compositions were stored (left stationary) in a container at 40°C for 30 days, and the viscosity increase rate (viscosity change rate) from the initial value was evaluated using an E-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.). Specifically, each evaluation composition was prepared, and the initial viscosity of the evaluation composition immediately after preparation was measured at 25°C for 3 minutes using an E-type rotational viscometer at a rotation speed of 2 rpm. Each evaluation composition was placed in a sealed container and stored in an oven at 40°C for 30 days, then cooled to 25°C. Similarly to the initial viscosity, the viscosity was measured for 3 minutes using an E-type rotational viscometer at a rotation speed of 2 rpm to obtain the viscosity after 30 days. Using the obtained initial viscosity and viscosity after 30 days, the viscosity increase rate was calculated according to the following formula (A) and evaluated according to the following evaluation criteria. The results are shown in Tables 4 to 6 below. Note that a lower viscosity increase rate indicates better storage stability. Viscosity increase rate (%) = [(viscosity after 30 days - initial viscosity) ÷ initial viscosity] × 100 (A)

[0308] <Composition for evaluation> Curing agent: parts by mass shown in Tables 4 to 6 Epoxy compound 1: 60 parts by mass Phosphoric acid-modified epoxy resin: 10 parts by mass Rubber-modified epoxy resin: 10 parts by mass Block urethane: 20 parts by mass Filler: 25 parts by mass Filler (thixotropic agent): 1 part by mass

[0309] <Evaluation criteria> 5: The viscosity increase rate is 50% or less. 4: The viscosity increase rate is more than 50% and 200% or less. 3: The viscosity increase rate is more than 200%. 2: The fluidity was lost more than 1 week and 30 days ago, and the product gelled and hardened. 1: The fluidity was lost within 1 week, and the product gelled and hardened.

[0310] 4. Low-Temperature Curing Property 2 The curing agents obtained in Examples 31 to 52 and Comparative Examples 31 to 40 were evaluated by differential scanning calorimetry (DSC measurement). Specifically, the evaluation compositions prepared in "3. Storage Stability 2" were subjected to DSC measurement under the following measurement conditions, and the peak top temperatures were measured. The results are shown in Tables 4 to 6 below. The peak top indicates the temperature at which the maximum heat release is observed within the scanning range. Note that the lower the peak top temperature, the better the low-temperature curing property can be determined.

[0311] (DSC measurement conditions) Apparatus: Q2000 (differential scanning calorimeter manufactured by TA Instruments) Heating rate: 3°C / min Operating temperature range: 30°C to 250°C

[0312] 5. Adhesion Using an iron test piece with one side polished as the adherend, the evaluation composition prepared in "3. Storage stability 2" according to JIS K 6854-3 was cured at 140°C for 30 minutes, and then the T-peel strength (kN / m) at 25°C was measured and evaluated according to the following evaluation criteria. The results are shown in Tables 4 to 6 below. Note that the higher the peel strength value, the better the adhesion. <Evaluation criteria> ◎: 7.0 kN / m or more ◯: 5.0 kN / m or more but less than 7.0 kN / m △: 2.0 kN / m or more but less than 5.0 kN / m ×: less than 2.0 kN / m

[0313]

[0314]

[0315]

[0316] [Summary] Tables 1 to 3 confirm that the use of the curing agent material of the Examples, i.e., Compound A, makes it possible to form curing agents with excellent low-temperature curing properties and storage stability. Tables 4 and 5 confirm that the use of the curing agent material of the Examples, i.e., Compound A, makes it possible to form curing agents with excellent low-temperature curing properties and storage stability. More specifically, compared to Comparative Example 40, it was confirmed that the Examples made it possible to form curing agents with excellent low-temperature curing properties and storage stability. Comparisons between Comparative Examples 31 and 32 and Examples 31 to 36 confirm that the use of Compound A makes it possible to form curing agents with excellent low-temperature curing properties compared to curing agents containing only anionic curing agents. Comparisons between Comparative Example 33 and Examples 37, 44 to 46 confirm that the use of Compound A makes it possible to form curing agents with excellent low-temperature curing properties compared to curing agents containing only anionic curing agents. A comparison of Comparative Example 34 with Examples 38, 47 to 49 confirmed that, compared to a curing agent containing only an anionic curing agent, the use of Compound A makes it possible to form a curing agent with excellent low-temperature curing properties. A comparison of Example 31 with Examples 32, 37, etc. confirmed that the use of ureas as an anionic curing agent in combination with Compound A makes it possible to form a cured product with excellent low-temperature curing properties, storage stability, and adhesiveness.

Claims

1. A curing agent material comprising a structural unit having a tertiary amine structural group and containing a compound having a weight average molecular weight of 5,000 or more and 30,000 or less.

2. The curing agent material according to claim 1, which is for use in combination with an anionic curing agent.

3. The curing agent material according to claim 1, wherein the tertiary amine structural group has a tertiary amino group.

4. The curing agent material according to claim 1, wherein the structural unit having a tertiary amine structural group has at least one of a hydroxyl group and a carboxyl group.

5. The curing agent material according to claim 1, wherein the structural unit having the tertiary amine structural group has a structural unit represented by the following general formula (100). (In the formula, R 101 and R 102 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following group B, L 1 represents a divalent group selected from -O-, -CO-, -CO-O-, -O-CO-, -CO-NR 103 -, and -NR 103 -CO-, R 103 represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, or a group in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following group B, L 2 represents a (c + 1)-valent hydrocarbon group having 1 to 20 carbon atoms, or a group in which a methylene group in the hydrocarbon group is substituted with a divalent group selected from the following group B, X 1 represents a tertiary amine structural group, group B represents -O-, -CO-, -CO-O-, -O-CO-, -NH-, -NHCO-, and -S-, a represents an integer of 0 or 1, b represents an integer of 0 or 1, c represents an integer of 1 to 10.) 6. The curing agent material according to claim 1, wherein the content of the structural unit having a tertiary amine structural group is 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the compound.

7. The curing agent material according to claim 4, wherein the compound has a structural unit derived from at least one compound selected from the group consisting of a hydroxyl group-containing ethylenically unsaturated compound, a carboxyl group-containing ethylenically unsaturated compound, and an aromatic unsaturated compound as a structural unit other than the structural unit having a tertiary amine structural group.

8. A curing agent comprising a compound containing a structural unit having a tertiary amine structural group and having a weight average molecular weight of 5,000 or more and 30,000 or less, and an anionic curing agent.

9. The curing agent according to claim 8, wherein the anionic curing agent contains an amine-based curing agent.

10. A curable composition comprising a compound containing a structural unit having a tertiary amine structural group and having a weight average molecular weight of 5,000 or more and 30,000 or less, and a curable compound.

11. The curable composition according to claim 10, which contains an anionic curing agent.

12. A cured product of the curable composition according to claim 11.

13. A method for producing a cured product, comprising a step of heating the curable composition according to claim 11.

14. A polymer having a bonding functional group b which is at least one kind of group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, and an amino group, and having a weight average molecular weight of 3,000 or more and 25,000 or less, and a compound having a bonding functional group c capable of reacting with the bonding functional group b to form a covalent bond and a tertiary amine structural group, the method for producing a curing agent material being characterized by having a reaction step of reacting them.

15. The method for producing a curing agent material according to claim 14, wherein the polymer has a structural unit derived from an unsaturated dicarboxylic acid or an unsaturated dicarboxylic anhydride as a structural unit having the bonding functional group b.

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