Compositions, hardeners, adhesives, rust inhibitors, resin compositions, cured products, resin pastes, resin films, printed circuit boards, semiconductor packaging, and electronic devices.

Abstract

This invention relates to a composition comprising: component (A): a compound represented by a specified formula (1) and / or a compound represented by a specified formula (2); and component (B): a compound having a structure that acts as a hydrogen bond acceptor (except for component (A)). (In formula (1), R1 and R2 are independently hydrogen atoms, hydroxyl groups, carboxyl groups, etc.; X is a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that may have substituents, etc.; Y is a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, etc.; m is an integer from 1 to 4) (In formula (2), X is a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that may have substituents, etc.; Y and Z are hydrogen atoms, halogen atoms, hydroxyl groups, carboxyl groups, etc.; m and n are independently integers from 1 to 4)

Description

[Technical Field]

[0001] This invention relates to a composition, a hardener, an adhesive, a rust inhibitor, a resin composition, a cured material, a resin paste, a resin film, a printed circuit board, a semiconductor package, and an electronic device. [Previous Technology]

[0002] Previously, imidazole compounds were known as useful compounds as hardeners or reaction promoters for various resins, such as epoxy resins, polyurethane resins, and cyclosulfide resins. Furthermore, imidazole compounds function by utilizing intramolecular nitrogen as a good ligand, and are useful in applications such as various adhesives or rust inhibitors. In addition, they are practical as intermediate raw materials for obtaining functional compounds such as pharmaceuticals or pesticides.

[0003] In particular, depending on its use as a curing agent, imidazole compounds with various functional groups are synthesized, and their structures are used to control the storage stability or reactivity of resin compositions containing the aforementioned imidazole compounds. For example, Patent Document 1 discloses an imidazole compound with excellent storage stability that selectively cures in a high-temperature region of 150°C. [Prior Art Documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2016-29152 [Summary of the Invention]

[0005] [Problem to be Solved by the Invention] In recent years, from a reliability point of view, resin compositions containing curable resins, such as epoxy resin, have been used in components used in electronic devices or electronic parts, such as in the assembly or mounting of semiconductor chips. These resin compositions, in the form of liquid resin pastes or film-shaped resin films, are used as adhesives, sealants, or insulators in electronic devices, and typically undergo a thermosetting process to perform the desired bonding, sealing, or insulating functions.

[0006] However, in increasingly sophisticated electronic devices and components, there are instances where components with lower heat resistance are used, necessitating manufacturing processes at low temperatures. Furthermore, bonding or sealing at high temperatures presents the following problems: due to thermal expansion, the dimensions of the component differ significantly between high-temperature and room-temperature conditions, leading to increased internal stress and a higher likelihood of defects such as poor connections caused by cracks. Moreover, from an environmental perspective, lower temperatures are required for the curing process to reduce energy consumption.

[0007] The imidazole compound disclosed in Patent Document 1 has good storage stability, but it is limited to high-temperature regions such as 150°C for curing. Therefore, it cannot be used in processes that require curing under low-temperature conditions as described above.

[0008] Therefore, in view of the aforementioned problems of the prior art, the object of the present invention is to provide a composition that provides a resin composition having sufficient storage stability and good curing properties in a low-temperature region below 150°C. [Technical Means for Solving the Problem]

[0009] Through dedicated research, the inventors discovered that by using a composition containing an imidazole compound having a specific structure and a compound having a structure that acts as a hydrogen bond acceptor, a resin composition with sufficient storage stability and good curing properties in a low-temperature region below 150°C can be obtained, thus completing the present invention. That is, the present invention is as follows.

[0010] [1] A composition comprising component (A): a compound represented by formula (1) below and / or a compound represented by formula (2) below, and component (B): a compound having a structure that is an acceptor of hydrogen bonds (except for component (A));

[0011] [Chemical 1]

[0012] In formula (1), R1 and R2 are each independently selected from the group consisting of hydrogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, halogen atoms, alkyl groups with 1 to 20 carbon atoms that may have substituents, and cycloalkyl groups with 6 to 20 carbon atoms that may have substituents. R1 and R2 may be the same or different. R1 and R2 may be bonded to form a fused ring that does not have aromaticity. X is selected from the group consisting of hydrogen atoms, alkyl groups with 1 to 20 carbon atoms that may have substituents, alkenyl groups with 2 to 20 carbon atoms that may have substituents, aralkyl groups with 7 to 20 carbon atoms that may have substituents, and heteroarylalkyl groups with 4 to 20 carbon atoms that may have substituents. Y is selected from any one of the following groups: hydrogen atom, halogen atom, hydroxyl group, carboxyl group, cyano group, nitro group, alkyl group with 1 to 20 carbon atoms that may have substituents, alkoxy group with 1 to 20 carbon atoms that may have substituents, alkenyl group with 2 to 20 carbon atoms that may have substituents, aryl group with 6 to 20 carbon atoms that may have substituents, aryloxy group with 6 to 20 carbon atoms that may have substituents, and acetyl group with 1 to 20 carbon atoms that may have substituents. When there are multiple Y groups, they may be the same or different. Two or more Y groups may be bonded together to form a monocyclic or fused ring. m is an integer from 1 to 4.

[0013] [Chemical 2]

[0014] In formula (2), X is any one selected from the group consisting of hydrogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkenyl groups having 2 to 20 carbon atoms that may have substituents, aralkyl groups having 7 to 20 carbon atoms that may have substituents, and heteroarylalkyl groups having 4 to 20 carbon atoms that may have substituents. Y and Z are selected from any one of the following groups: hydrogen atom, halogen atom, hydroxyl group, carboxyl group, cyano group, nitro group, alkyl group with 1 to 20 carbon atoms that may have substituents, alkoxy group with 1 to 20 carbon atoms that may have substituents, alkenyl group with 2 to 20 carbon atoms that may have substituents, aryl group with 6 to 20 carbon atoms that may have substituents, aryloxy group with 6 to 20 carbon atoms that may have substituents, and acetyl group with 1 to 20 carbon atoms that may have substituents. Y and Z may be the same or different. Two or more Y groups and two or more Z groups may be bonded together to form a monocyclic or fused ring. m and n are each an integer from 1 to 4.

[0015] [2] The composition of [1] above, wherein the content of the above component (B) is less than 10,000 ppm relative to the total mass of the above component (A) and the above component (B). [3] The composition of [1] or [2] above, wherein the content of the above component (B) is 50 ppm or more relative to the total mass of the above component (A) and the above component (B). [4] The composition of any one of [1] to [3] above, wherein the above component (B) contains at least one compound with a structure selected from the group consisting of formula (3), formula (4) and formula (5) below;

[0016] [Chemical 3]

[0017] In formula (3), the ・・ on the nitrogen atom represents a non-shared electron pair;

[0018] [Chemical 4]

[0019] In formula (4), the ・・ on the nitrogen atom represents a non-shared electron pair;

[0020] [Chemical 5]

[0021] In formula (5), the ・・ on the phosphorus atom represents a non-shared electron pair.

[0022] [5] The composition of [4] above, wherein the component (B) is a compound containing the structure of formula (3) and formula (4) above. [6] The composition of [4] or [5] above, wherein the component (B) is an aromatic heterocyclic amine containing the structure of formula (3) and formula (4) above. [7] The composition of any one of [1] to [6] above, wherein the component (B) contains an imidazole compound. [8] The composition of any one of [1] to [7] above, wherein the component (B) contains one or more of the group consisting of imidazole, 4-methylimidazolium, 2-ethyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 4-ethyl-5-methylimidazolium, 4-butyl-5-methylimidazolium, and 2,2'-biimidazole. [9] A composition of any one of [1] to [8] above, wherein the molecular weight of the above component (B) is 50,000 or less.

[10] A composition of any one of [1] to [9] above, wherein in the above formula (1), Y is selected from the group consisting of hydrogen atom, hydroxyl group, carboxyl group, alkoxy group with 1 to 20 carbon atoms without substituents, alkyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, alkoxy group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, aryl group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, aryloxy group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, and acetyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents. In the above formula (2), Y and Z are selected from one of the group consisting of hydrogen atom, hydroxyl group, carboxyl group, alkoxy group with 1 to 20 carbon atoms without substituents, alkyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, alkoxy group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, aryl group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, aryloxy group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, and acetyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents.

[11] The composition of any one of [1] to

[10] above, wherein in the above component (A), the compound represented by the above formula (1) is selected from any one of the group consisting of 2-(2-hydroxyphenyl)imidazole, 2-(2-hydroxyphenyl)-4(5)-methylimidazole, 4-ethyl-(2-hydroxyphenyl)-5-methylimidazole, (2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxyphenyl)-5-methylimidazole, and 2-(2-hydroxy-3(5)-methoxyphenyl)imidazole. And / or the compound represented by formula (2) above is selected from any one of the group consisting of 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole, 2-(3-tert-butyl-2-hydroxyphenyl)-5(6)-methylbenzimidazole, 2-(3-tert-butyl-5-tert-butyl-2-hydroxyphenyl)benzimidazole, 2-(3-tert-butyl-5-tert-butyl-2-hydroxyphenyl)-5(6)-methylbenzimidazole, 2-(1-hydroxynaphthyl-2-yl)benzimidazole, 2-(2-hydroxynaphthyl-1-yl)benzimidazole, and 2-(2-hydroxyphenyl)benzimidazole-6-carboxylic acid.

[12] A curing agent comprising a composition as described in any one of [1] to

[11] above.

[13] An adhesive comprising a composition of any one of [1] to

[11] above.

[14] A rust inhibitor comprising a composition of any one of [1] to

[11] above.

[15] A resin composition comprising a composition of any one of [1] to

[11] above and a curing resin.

[16] A resin composition of

[15] above, wherein the curing resin comprises an epoxy resin.

[17] A resin composition of

[16] above, wherein the epoxy resin comprises an epoxy resin that is liquid at 25°C.

[18] A cured material, which is a cured product of a resin composition of any one of

[15] to

[17] above.

[19] A resin paste comprising a resin composition of any one of

[15] to

[17] above.

[20] A resin film comprising a resin composition of any one of

[15] to

[17] above.

[21] A printed circuit board having a hardened layer comprising a hardened resin composition as described in any one of

[15] to

[17] above.

[22] A semiconductor package having a hardened layer comprising a hardened resin composition as described in any one of

[15] to

[17] above.

[23] An electronic device having a printed circuit board as described in

[21] above.

[24] An electronic device having a semiconductor package as described in

[22] above. [Effects of the Invention].

[0023] According to the present invention, a resin composition having sufficient storage stability and good curing properties in a low temperature range below 150°C can be obtained.

Implementation Method

[0024] Hereinafter, a method for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. The following embodiments are for illustrating the present invention and are not intended to limit the present invention to the following content. The present invention may be implemented with appropriate changes within its scope.

[0025] [Composition] The composition of this embodiment contains component (A): the compound represented by formula (1) below and / or the compound represented by formula (2) below, and component (B): the compound other than component (A) above that has a structure that can become a hydrogen bond acceptor.

[0026] By using the resin composition of this embodiment with the above-described structure, sufficient storage stability can be achieved, and good curing properties can be exhibited in low-temperature regions below 150°C.

[0027] (Component (A): The compound represented by formula (1) or (2) below) The composition of this embodiment contains the compound represented by formula (1) below and / or the compound represented by formula (2) below (hereinafter, sometimes referred to as compound (A) or component (A)).

[0028] [Chemical 6]

[0029] In formula (1), R1 and R2 are each independently selected from the group consisting of hydrogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, halogen atoms, alkyl groups with 1 to 20 carbon atoms that may have substituents, and cycloalkyl groups with 6 to 20 carbon atoms that may have substituents. R1 and R2 may be the same or different. R1 and R2 may be bonded to form a fused ring that does not have aromaticity. X is selected from the group consisting of hydrogen atoms, alkyl groups with 1 to 20 carbon atoms that may have substituents, alkenyl groups with 2 to 20 carbon atoms that may have substituents, aralkyl groups with 7 to 20 carbon atoms that may have substituents, and heteroarylalkyl groups with 4 to 20 carbon atoms that may have substituents. Y is selected from any one of the following groups: hydrogen atom, halogen atom, hydroxyl group, carboxyl group, cyano group, nitro group, alkyl group with 1 to 20 carbon atoms that may have substituents, alkoxy group with 1 to 20 carbon atoms that may have substituents, alkenyl group with 2 to 20 carbon atoms that may have substituents, aryl group with 6 to 20 carbon atoms that may have substituents, aryloxy group with 6 to 20 carbon atoms that may have substituents, and acetyl group with 1 to 20 carbon atoms that may have substituents. When there are multiple Y groups, they may be the same or different. Two or more Y groups may be bonded to form a monocyclic or fused ring. m is an integer from 1 to 4.

[0030] [Chemical 7]

[0031] In formula (2), X is any one of the group consisting of hydrogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkenyl groups having 2 to 20 carbon atoms that may have substituents, aralkyl groups having 7 to 20 carbon atoms that may have substituents, and heteroarylalkyl groups having 4 to 20 carbon atoms that may have substituents. Y and Z are selected from any one of the following groups: hydrogen atom, halogen atom, hydroxyl group, carboxyl group, cyano group, nitro group, alkyl group with 1 to 20 carbon atoms that may have substituents, alkoxy group with 1 to 20 carbon atoms that may have substituents, alkenyl group with 2 to 20 carbon atoms that may have substituents, aryl group with 6 to 20 carbon atoms that may have substituents, aryloxy group with 6 to 20 carbon atoms that may have substituents, and acetyl group with 1 to 20 carbon atoms that may have substituents. Y and Z may be the same or different. Two or more Y groups and two or more Z groups may be bonded together to form a monocyclic or fused ring. m and n are each an integer from 1 to 4.

[0032] In the above general formula (1), R1 and R2 are, as described above, independently selected from one of the group consisting of hydrogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, halogen atoms, alkyl groups with 1 to 20 carbon atoms that may have substituents, and cycloalkyl groups with 6 to 20 carbon atoms that may have substituents, or a structure in which R1 and R2 are on the same condensed ring that does not have aromaticity. R1 and R2 may be the same or different. The alkyl group with 1 to 20 carbon atoms may be chain-like or branched. The number of carbon atoms of the alkyl group is preferably 1 to 18, more preferably 1 to 15, and even more preferably 1 to 10. There is no particular limitation on the alkyl group with 1 to 20 carbon atoms. Examples include: methyl, ethyl, isopropyl, butyl, isobutyl, tributyl, hexyl, octyl, 2-ethylhexyl, etc. The number of carbon atoms in a cycloalkyl group having 6 to 20 carbon atoms is preferably 6 to 18, more preferably 6 to 15. There is no particular limitation on the cycloalkyl group having 6 to 20 carbon atoms; examples include cyclohexyl, cycloheptyl, and cyclooctyl. Examples of structures where R1 and R2 are located on the same non-aromatic condensed ring include cyclopentane, cyclohexane, and dicyclopentadiene. Furthermore, the structures where the alkyl group, cycloalkyl group, and R1 and R2 are located on the same non-aromatic fused ring may have substituents. Substituents are not limited to the following; examples include halogen atoms, hydroxyl groups, alkoxy groups, and nitro groups, with hydroxyl and alkoxy groups being more preferred.

[0033] X in the above formulas (1) and (2) is any one of the group consisting of hydrogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkenyl groups having 2 to 20 carbon atoms that may have substituents, aralkyl groups having 7 to 20 carbon atoms that may have substituents, and heteroarylalkyl groups having 4 to 20 carbon atoms that may have substituents.

[0034] The alkyl group having 1 to 20 carbon atoms as described above can be chain-like or branched. The number of carbon atoms as the alkyl group is preferably 1 to 18, and more preferably 1 to 15. The alkyl group having 1 to 20 carbon atoms is not limited to the following, and examples include: methyl, ethyl, isopropyl, butyl, isobutyl, tributyl, hexyl, octyl, etc.

[0035] The alkenyl group having 2 to 20 carbon atoms as described above can be chain-like or branched. The number of carbon atoms in the alkenyl group is preferably 2 to 18, and more preferably 2 to 15. The alkenyl group having 2 to 20 carbon atoms is not limited to the following, and examples include: vinyl, aryl, 1-propenyl, isopropenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 2-hexenyl, etc.

[0036] The aryl group having 7 to 20 carbon atoms as X above can be chain-like or branched. The number of carbon atoms as aryl group is preferably 7 to 18, and more preferably 7 to 15. The aryl group having 7 to 20 carbon atoms is not limited to the following, for example: benzyl, phenethyl, naphthylmethyl, etc.

[0037] The heteroaryl alkyl group having 4 to 20 carbon atoms as described above can be chain-like or branched. The number of carbon atoms in the heteroaryl alkyl group is preferably 4 to 18, more preferably 4 to 15. The heteroaryl alkyl group having 4 to 20 carbon atoms is not limited to the following, but examples include: trimethylol, trimethylolethyl, 2-pyridylmethyl, 2-pyridylethyl, 3-pyridylmethyl, 3-pyridylethyl, 4-pyridylmethyl, 4-pyridylethyl, etc.

[0038] Furthermore, the aforementioned alkyl, alkenyl, aralkyl, or heteroarylalkyl groups may be substituents. Substituents are not limited to the following, for example: halogen atom, cyano, nitro, hydroxyl, alkoxy, amino, ester, arylsulfonyl, alkylsulfonyl, phenyl, etc., preferably cyano, alkoxy, amino, ester, or phenyl.

[0039] Y in the above general formula (1) and Y and Z in the above general formula (2) are selected from any one of the group consisting of hydrogen atom, halogen atom, hydroxyl group, carboxyl group, cyano group, nitro group, alkyl group with 1 to 20 carbon atoms that may have substituents, alkoxy group with 1 to 20 carbon atoms that may have substituents, alkenyl group with 2 to 20 carbon atoms that may have substituents, aryl group with 6 to 20 carbon atoms that may have substituents, aryloxy group with 6 to 20 carbon atoms that may have substituents, and acetyl group with 1 to 20 carbon atoms that may have substituents. Furthermore, in the above general formula (1), two or more Y atoms can be bonded to form a monocyclic or fused ring. Furthermore, in the above general formula (2), two or more Y atoms and two or more Z atoms can be bonded to form a monocyclic or fused ring. Furthermore, in the above general formula (1), m is an integer from 1 to 4. Furthermore, in the above general formula (2), m and n are independent integers from 1 to 4.

[0040] The alkyl group having 1 to 20 carbon atoms in Y and Z above can be chain-like or branched. The number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 15. The alkyl group having 1 to 20 carbon atoms is not limited to the following, and examples include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tributyl, hexyl, octyl, 2-ethylhexyl, decyl, undecyl, etc.

[0041] The alkoxy group of Y and Z with 1 to 20 carbon atoms can be chain-like or branched. The number of carbon atoms is preferably 1 to 18, more preferably 1 to 15. The alkoxy group with 1 to 20 carbon atoms is not limited to the following, for example: methoxy, ethoxy, propoxy, isopropoxy, butoxy, hexoxy, 2-ethylhexoxy, etc.

[0042] The alkenyl group having 2 to 20 carbon atoms in Y and Z can be chain-like or branched. The number of carbon atoms in the alkenyl group is preferably 2 to 18, and more preferably 2 to 15. The alkenyl group having 2 to 20 carbon atoms is not limited to the following, and examples include: vinyl, aryl, 1-propenyl, isopropenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 2-hexenyl, etc.

[0043] As for the number of carbons of the aryl group with 6 to 20 carbons in Y and Z mentioned above, it is preferably 6 to 18, and more preferably 6 to 15. The aryl group with 6 to 20 carbons is not limited to the following, for example: phenyl, naphthyl, anthracene, biphenyl, etc.

[0044] Furthermore, the structure formed by two or more Y or two or more Z bonds to form a monocyclic or fused ring is not limited to the following, for example: naphthyl, anthracene, etc.

[0045] As for the number of carbons of the acetoyl group of Y and Z with 1 to 20 carbons, it is preferably 1 to 18, more preferably 1 to 15. The acetoyl group with 1 to 20 carbons is not limited to the following, for example: acetoyl, benzoyl, trimethylacetoyl, etc.

[0046] Furthermore, the above-mentioned alkyl, alkoxy, alkenyl, aryl, aryloxy and acetyl groups may be those with substituents. Examples of substituents include: alkyl, halogen, hydroxyl, carboxyl, alkoxy, nitro, ester, phenyl, etc., with alkyl, hydroxyl, carboxyl and alkoxy being more preferred.

[0047] Y can be a phenyl group that is substituted at the ortho, meta, or para position as a substituent at the 2-position of the imidazole. In the case of a substituent, it is more preferably substituted at a position other than the ortho position, and even more preferably substituted at least at the meta position. More preferably, it is substituted at the meta position by a hydroxyl group or by an alkoxy group having 1 to 20 carbon atoms.

[0048] In the above, in formula (1), Y is preferably selected from one of the group consisting of hydrogen atom, hydroxyl group, carboxyl group, alkoxy group with 1 to 20 carbon atoms without substituents, alkyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, alkoxy group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, aryl group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, aryloxy group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, and acetyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents. Furthermore, in formula (2) above, Y and Z are preferably selected from one of the following groups: hydrogen atom, hydroxyl group, carboxyl group, alkoxy group with 1 to 20 carbon atoms without substituents, alkyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, alkoxy group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, aryl group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, aryloxy group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, and acetyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents. By making Y and Z hydrogen atoms, steric hindrance is reduced, and the composition of this embodiment tends to maintain a high reactivity when formulated with a curing resin, or to improve adhesion or bonding strength because it is easy to form coordination bonds with the substrate such as a metal. Furthermore, when Y and Z are hydroxyl, carboxyl, alkoxy group with 1 to 20 carbon atoms without substituents, alkyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl as substituents, alkoxy group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl as substituents, aryl group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl as substituents, aryloxy group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl as substituents, or acetyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl as substituents, the coordination bonding of the composition of this embodiment to the substrate such as metal increases, thus tending to improve adhesion or bonding strength.

[0049] The compound represented by the above general formula (1) is not limited to the following, for example, the following imidazole compounds can be cited. For example, 2-(2-hydroxyphenyl)imidazolium, 2-(2-hydroxyphenyl)-4(5)-methylimidazolium, 4(5)-ethyl-2-(2-hydroxyphenyl)imidazolium, 4,5-dimethyl-2-(2-hydroxyphenyl)imidazolium, 4-ethyl-(2-hydroxyphenyl)-5-methylimidazolium, (2-hydroxyphenyl)-4-isopropyl-5-methylimidazolium, 4-butyl-(2-hydroxyphenyl)-5-methylimidazolium, 2-(2-hydroxy-3-methylphenyl)imidazolium, 2-(2-hydroxy-3-methylphenyl)-4(5)-methylimidazolium, 4(5)- Ethyl-2-(2-hydroxy-3-methylphenyl)imidazolium, 4,5-dimethyl-2-(2-hydroxy-3-methylphenyl)imidazolium, 4-ethyl-(2-hydroxy-3-methylphenyl)-5-methylimidazolium, (2-hydroxy-3-methylphenyl)-4-isopropyl-5-methylimidazolium, 4-butyl-(2-hydroxy-3-methylphenyl)-5-methylimidazolium, 2-(2-hydroxy-4-methylphenyl)imidazolium, 2-(2-hydroxy-4-methylphenyl)-4(5)-methylimidazolium, 4(5)-ethyl-2-(2-hydroxy-4-methylphenyl)imidazolium.

[0050] Also, examples include: 4,5-dimethyl-2-(2-hydroxy-4-methylphenyl)imidazolium, 4-ethyl-(2-hydroxy-4-methylphenyl)-5-methylimidazolium, (2-hydroxy-4-methylphenyl)-4-isopropyl-5-methylimidazolium, 4-butyl-(2-hydroxy-4-methylphenyl)-5-methylimidazolium, 2-(2-hydroxy-5-methylphenyl)imidazolium, 2-(2-hydroxy-5-methylphenyl)-4(5)-methylimidazolium, 4(5)-ethyl-2-(2-hydroxy-5-methylphenyl) Imidazole, 4,5-dimethyl-2-(2-hydroxy-5-methylphenyl)imidazol, 4-ethyl-(2-hydroxy-5-methylphenyl)-5-methylimidazol, (2-hydroxy-5-methylphenyl)-4-isopropyl-5-methylimidazol, 4-butyl-(2-hydroxy-5-methylphenyl)-5-methylimidazol, 2-(3-tert-butyl-2-hydroxyphenyl)imidazol, 2-(3-tert-butyl-2-hydroxyphenyl)-4(5)-methylimidazol, 2-(3-tert-butyl-2-hydroxyphenyl)-4(5)-ethylimidazol.

[0051] Furthermore, examples include: 2-(3-tert-butyl-2-hydroxyphenyl)-4,5-dimethylimidazolium, 2-(3-tert-butyl-2-hydroxyphenyl)-4-ethyl-5-methylimidazolium, 2-(3-tert-butyl-2-hydroxyphenyl)-4-isopropyl-5-methylimidazolium, 4-butyl-2-(3-tert-butyl-2-hydroxyphenyl)-5-methylimidazolium, 2-(4-fluoro-2-hydroxyphenyl)imidazolium, 2-(4-fluoro-2-hydroxyphenyl)-4(5)-methyl ... 4-(5)-ethylimidazole, 2-(4-fluoro-2-hydroxyphenyl)-4,5-dimethylimidazole, 4-ethyl-2-(4-fluoro-2-hydroxyphenyl)-5-methylimidazole, 2-(4-fluoro-2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-2-(4-fluoro-2-hydroxyphenyl)-5-methylimidazole, 2-(4-chloro-2-hydroxyphenyl)imidazole, 2-(4-chloro-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(4-chloro-2-hydroxyphenyl)-4(5)-ethylimidazole.

[0052] Further examples include: 2-(4-chloro-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(4-chloro-2-hydroxyphenyl)-4-ethyl-5-methylimidazole, 2-(4-chloro-2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-2-(4-chloro-2-hydroxyphenyl)-5-methylimidazole, 2-(4-bromo-2-hydroxyphenyl)imidazole, 2-(4-bromo-2-hydroxyphenyl)-4( 5)-Methylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4(5)-ethylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4-ethyl-5-methylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4-butyl-5-methylimidazole, 2-(2,3-dihydroxyphenyl)imidazole.

[0053] Further examples include: 2-(2,3-dihydroxyphenyl)-4(5)-methylimidazole, 2-(2,3-dihydroxyphenyl)-4(5)-ethylimidazole, 2-(2,3-dihydroxyphenyl)-4,5-dimethylimidazole, 2-(2,3-dihydroxyphenyl)-4(5)-phenylimidazole, 2-(2,3-dihydroxyphenyl)-4,5-diphenylimidazole, 2-(2,5-dihydroxyphenyl)imidazole, 2-(2,5-dihydroxyphenyl)-4(5)-methylimidazole, 2-(2,5-dihydroxyphenyl)-4(5)-ethylimidazole, 2-(2,5-dihydroxyphenyl)-4,5-dimethylimidazole, 2-(2,5-dihydroxyphenyl)-4(5)-phenylimidazole, 2- (2,5-Dihydroxyphenyl)-4,5-Diphenylimidazole, 2-(2-hydroxy-4-methoxyphenyl)imidazole, 2-(2-hydroxy-4-methoxyphenyl)-4(5)-methylimidazole, 4(5)-ethyl-2-(2-hydroxy-4-methoxyphenyl)imidazole, 4,5-dimethyl-2-(2-hydroxy-4-methoxyphenyl)imidazole, 2-(2-hydroxy-4-methoxyphenyl)-4(5)-phenylimidazole, 4,5-diphenyl-2-(2-hydroxy-4-methoxyphenyl)imidazole, 2-(2-hydroxy-3-methoxyphenyl)imidazole, 2-(2-hydroxy-3-methoxyphenyl)-4(5)-methylimidazole, 4(5)-ethyl-2-(2-hydroxy-3-methoxyphenyl)imidazole.

[0054] Also, examples include: 4,5-dimethyl-2-(2-hydroxy-3-methoxyphenyl)imidazolium, 2-(2-hydroxy-3-methoxyphenyl)-4(5)-phenylimidazolium, 4,5-diphenyl-2-(2-hydroxy-3-methoxyphenyl)imidazolium, 2-(2-hydroxy-5-methoxyphenyl)imidazolium, 2-(2-hydroxy-5-methoxyphenyl)-4(5)-methylimidazolium, 4(5)-ethyl-2-(2-hydroxy-5-methoxyphenyl)imidazolium, 4,5-dimethyl-2-(2-hydroxy-5-methoxyphenyl)imidazolium, 2-(2-hydroxy-5-methoxyphenyl)-4(5)-phenylimidazolium, 4,5-diphenyl-2-(2-hydroxy-5-methoxyphenyl)imidazolium, 2-(2-hydroxy-6-methoxyphenyl)imidazolium Imidazole, 2-(2-hydroxy-6-methoxyphenyl)-4(5)-methylimidazole, 4(5)-ethyl-2-(2-hydroxy-6-methoxyphenyl)imidazole, 4,5-dimethyl-2-(2-hydroxy-6-methoxyphenyl)imidazole, 2-(2-hydroxy-6-methoxyphenyl)-4(5)-phenylimidazole, 4,5-diphenyl-2-(2-hydroxy-6-methoxyphenyl)imidazole, 2-(3-ethoxy-2-hydroxyphenyl)imidazole, 2-(3-ethoxy-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(3-ethoxy-2-hydroxyphenyl)-4(5)-ethylimidazole, 4,5-dimethyl-2-(3-ethoxy-2-hydroxyphenyl)imidazole, 2-(3-ethoxy-2-hydroxyphenyl)-4(5)-phenylimidazole.

[0055] Furthermore, examples include: 4,5-diphenyl-2-(3-ethoxy-2-hydroxyphenyl)imidazolium, 2-(5-ethoxy-2-hydroxyphenyl)imidazolium, 2-(5-ethoxy-2-hydroxyphenyl)-4(5)-methylimidazolium, 2-(5-ethoxy-2-hydroxyphenyl)-4(5)-ethylimidazolium, 4,5-dimethyl-2-(5-ethoxy-2-hydroxyphenyl)imidazolium, 2-(5-ethoxy-2-hydroxyphenyl)-4(5)-phenylimidazolium, 4,5-diphenyl-2-(5-ethoxy-2-hydroxyphenyl)imidazolium, 2-(4-allyl) -2-hydroxy-3-methoxyphenyl)imidazolium, 2-(4-allyl-2-hydroxy-3-methoxyphenyl)-4(5)-methylimidazolium, 2-(4-allyl-2-hydroxy-3-methoxyphenyl)-4(5)-ethylimidazolium, 2-(4-allyl-2-hydroxy-3-methoxyphenyl)-4,5-dimethylimidazolium, 2-(4-allyl-2-hydroxy-3-methoxyphenyl)-4(5)-phenylimidazolium, 2-(4-allyl-2-hydroxy-3-methoxyphenyl)-4,5-diphenylimidazolium, 2-(4,6-dimethoxy-2-hydroxyphenyl)imidazolium.

[0056] Further examples include: 2-(4,6-dimethoxy-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(4,6-dimethoxy-2-hydroxyphenyl)-4(5)-ethylimidazole, 2-(4,6-dimethoxy-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(4,6-dimethoxy-2-hydroxyphenyl)-4(5)-phenylimidazole, 2-(4,6-dimethoxy-2-hydroxyphenyl)-4,5-diphenylimidazole, 2-(2-fluoro-5-hydroxyphenyl)imidazole, 2-(2- Fluoro-5-hydroxyphenyl)-4(5)-methylimidazole, 2-(2-fluoro-5-hydroxyphenyl)-4(5)-ethylimidazole, 2-(2-fluoro-5-hydroxyphenyl)-4,5-dimethylimidazole, 2-(2-fluoro-5-hydroxyphenyl)-4(5)-phenylimidazole, 2-(2-fluoro-5-hydroxyphenyl)-4,5-diphenylimidazole, 2-(5-fluoro-2-hydroxyphenyl)imidazole, 2-(5-fluoro-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(5-fluoro-2-hydroxyphenyl)-4(5)-ethylimidazole.

[0057] Furthermore, examples include: 2-(5-fluoro-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(5-fluoro-2-hydroxyphenyl)-4(5)-phenylimidazole, 2-(5-fluoro-2-hydroxyphenyl)-4,5-diphenylimidazole, 2-(5-chloro-2-hydroxyphenyl)imidazole, 2-(5-chloro-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(5-chloro-2-hydroxyphenyl)-4(5)-ethylimidazole, 2-(5-chloro-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(5-chloro-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(5-chloro-2-hydroxyphenyl)-4 (5)-Phenylidene imidazole, 2-(5-chloro-2-hydroxyphenyl)-4,5-diphenylimidazolium, 2-(5-bromo-2-hydroxyphenyl)imidazolium, 2-(5-bromo-2-hydroxyphenyl)-4(5)-methylimidazolium, 2-(5-bromo-2-hydroxyphenyl)-4(5)-ethylimidazolium, 2-(5-bromo-2-hydroxyphenyl)-4,5-dimethylimidazolium, 2-(5-bromo-2-hydroxyphenyl)-4(5)-phenylimidazolium, 2-(5-bromo-2-hydroxyphenyl)-4,5-diphenylimidazolium, 2-(6-fluoro-2-hydroxy-3-methoxyphenyl)imidazolium.

[0058] Also, examples include: 2-(6-fluoro-2-hydroxy-3-methoxyphenyl)-4(5)-methylimidazolium, 2-(6-fluoro-2-hydroxy-3-methoxyphenyl)-4(5)-ethylimidazolium, 2-(6-fluoro-2-hydroxy-3-methoxyphenyl)-4,5-dimethylimidazolium, 2-(6-fluoro-2-hydroxy-3-methoxyphenyl)-4(5)-phenylimidazolium, 2-(6-fluoro-2-hydroxy-3-methoxyphenyl)-4,5-diphenylimidazolium, 2-(1-hydroxynaphthyl-2-yl)imidazolium, 2-(1-hydroxynaphthyl-2-yl)-4(5)-methyl ... )-4(5)-ethylimidazole, 4,5-dimethyl-2-(1-hydroxynaphth-2-yl)imidazole, 2-(1-hydroxynaphth-2-yl)-4(5)-phenylimidazole, 4,5-diphenyl-2-(1-hydroxynaphth-2-yl)imidazole, 2-(2-hydroxynaphth-1-yl)imidazole, 2-(2-hydroxynaphth-1-yl)-4(5)-methylimidazole, 2-(2-hydroxynaphth-1-yl)-4(5)-ethylimidazole, 4,5-dimethyl-2-(2-hydroxynaphth-1-yl)imidazole, 2-(2-hydroxynaphth-1-yl)-4(5)-phenylimidazole, 4,5-diphenyl-2-(2-hydroxynaphth-1-yl)imidazole, etc.

[0059] The compound represented by the above general formula (2) is not limited to the following, for example, the following imidazole compounds can be cited. For example, 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3-methylphenyl)benzimidazole, 2-(2-hydroxy-4-methylphenyl)benzimidazole, 2-(2-hydroxy-5-methylphenyl)benzimidazole, 2-(3-tert-butyl-2-hydroxyphenyl)benzimidazole, 2-(3-tert-butyl-2-hydroxyphenyl)-5(6)-methylbenzimidazole, 2-(3-tert-butyl-5-tert-butyl-2- 2-(3-tert-butyl-5-tert-butyl-2-hydroxyphenyl)-5(6)-methylbenzimidazole, 2-(4-fluoro-2-hydroxyphenyl)benzimidazole, 2-(4-chloro-2-hydroxyphenyl)benzimidazole, 2-(4-bromo-2-hydroxyphenyl)benzimidazole, 2-(2,3-dihydroxyphenyl)benzimidazole, 2-(2,5-dihydroxyphenyl)benzimidazole, 2-(2-hydroxy-4-methoxy)benzimidazole 2-(2-hydroxy-3-methoxyphenyl)benzimidazole, 2-(2-hydroxy-5-methoxyphenyl)benzimidazole, 2-(2-hydroxy-6-methoxyphenyl)benzimidazole, 2-(3-ethoxy-2-hydroxyphenyl)benzimidazole, 2-(5-ethoxy-2-hydroxyphenyl)benzimidazole, 2-(4-allyl-2-hydroxy-3-methoxyphenyl)benzimidazole, 2-(4,6-dimethoxyphenyl)benzimidazole 2-(5-fluoro-2-hydroxyphenyl)benzimidazole, 2-(5-chloro-2-hydroxyphenyl)benzimidazole, 2-(5-bromo-2-hydroxyphenyl)benzimidazole, 2-(6-fluoro-2-hydroxy-3-methoxyphenyl)benzimidazole, 2-(1-hydroxynaphthyl-2-yl)benzimidazole, 2-(2-hydroxynaphthyl-1-yl)benzimidazole, 2-(2-hydroxyphenyl)benzimidazole-6-carboxylic acid, etc.

[0060] Among these, from the viewpoint that a uniform resin composition can be obtained by means of excellent solubility in resins or solvents, the compound represented by the above general formula (1) is preferably one in which R1 and R2 are both hydrogen atoms or have different substituents, for example more preferably 2-(2-hydroxyphenyl)imidazolium, 2-(2-hydroxyphenyl)-4(5)-methylimidazolium, 4-ethyl-2-(2-hydroxyphenyl)-5-methylimidazolium, 2-(2-hydroxyphenyl)-4-isopropyl-5-methylimidazolium, 4-butyl-2-(2-hydroxyphenyl)-5-methylimidazolium, 2-(2-hydroxy-3(5)-methoxyphenyl)imidazolium, and even more preferably 2-(2-hydroxyphenyl)imidazolium and 4-ethyl-2-(2-hydroxyphenyl)-5-methylimidazolium. Furthermore, from the viewpoint of achieving the same effect, the compounds represented by the above general formula (2) are preferably 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole, 2-(3-tert-butyl-2-hydroxyphenyl)-5(6)-methylbenzimidazole, 2-(3-tert-butyl-5-tert-butyl-2-hydroxyphenyl)benzimidazole, 2-(3-tert-butyl-5-tert-butyl-2-hydroxyphenyl)benzimidazole, and 2-(3-tert-butyl-5-tert-butyl-2-hydroxyphenyl)benzimidazole. -5-tert-butyl-2-hydroxyphenyl)-5(6)-methylbenzimidazole, 2-(1-hydroxynaphth-2-yl)benzimidazole, 2-(2-hydroxynaphth-1-yl)benzimidazole, 2-(2-hydroxyphenyl)benzimidazole-6-carboxylic acid, more preferably 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole, 2-(2-hydroxynaphth-1-yl)benzimidazole.

[0061] Component (A) has a structural characteristic of having a hydroxyphenyl substituted at the 2-position of an imidazole structure, which is reactive with various functional groups represented by epoxy groups or has the ability to coordinate with metals. Therefore, component (A) and the composition of this embodiment containing component (A) have excellent compatibility with resins or polar solvents containing aromatic rings, and are well soluble in various resins or solvents, making them a preferred component for use as a hardener, adhesion promoter, or rust inhibitor.

[0062] From the viewpoint of using component (A) as a curing agent or reaction promoter, an intramolecular hydrogen bond is formed between the nitrogen at the reaction site of imidazole and the adjacent hydroxyphenyl group. This suppresses the nucleophilicity of the nitrogen on the imidazole during storage, resulting in greater stability. However, the hydrogen bond can dissociate and react upon heating, making it a latent curing agent component. Furthermore, it is believed that the hydroxyphenyl group provides a proton, thus stabilizing the reaction intermediate. Taking epoxy resin as an example, the reaction intermediate generated when the epoxy group reacts with imidazole to open the ring, i.e., the anion, is stabilized by the nearby hydroxyphenyl group providing a proton. Therefore, suppressing the rapid reaction between epoxy groups results in a uniform chain extension reaction. Consequently, the cured resin composition obtained is less likely to retain unreacted monomers, exhibiting excellent heat resistance or strength.

[0063] Imidazole compounds, which are generally used as curing agents or reaction promoters, are known to have high stability. Solid-dispersed imidazole compounds, which have reduced compatibility with resins such as epoxy resins, are known to have reduced curing uniformity due to their solid nature. Furthermore, there are concerns that, especially in resin pastes where filling narrow gaps occurs, clogging can reduce filling capacity; or in resin films where solvents are mixed for film formation, particle residue can reduce film-forming properties, making them unsuitable for ultrathin films. Depending on the solvent, even solid-dispersed compounds may dissolve, resulting in a lack of stability. Therefore, components (A) described above, which can dissolve uniformly in resins or solvents while maintaining stability and reactivity, are particularly advantageous for applications such as resin pastes used to fill narrow gaps or resin films formed using solvents.

[0064] As an adhesion promoter or rust inhibitor for substrates represented by metals, the imidazole structure participates in the interaction with metal oxides or hydroxyl groups present on the surface of the substrate, forming coordinate bonds or hydrogen bonds. In addition, hydroxyphenyl groups can also participate in hydrogen bonding, thus interacting more strongly with the substrate, thereby tending to further improve adhesion. Furthermore, through the aforementioned stronger interaction, the imidazole compound arranges itself on the surface of the substrate, functioning as a protective layer, thus tending to further prevent metal from rusting.

[0065] Based on the above mechanism, if the component (A) represented by general formula (1) and / or (2) has structural features such as a hydroxyphenyl substituted at the 2-position of imidazole, it is considered that the component including those substituted with various functional groups can be widely and better used as a component of hardener, adhesion promoter, or rust inhibitor.

[0066] (Component (B): A compound having a structure that serves as a hydrogen bond acceptor) The composition of this embodiment contains component (B): a compound having a structure that serves as a hydrogen bond acceptor (except for component (A)). Here, a compound having a structure that serves as a hydrogen bond acceptor refers to a compound containing one or more atoms with non-shared electron pairs in its molecule, or a onium salt formed by coordination bonding with other cationic compounds through the aforementioned non-shared electron pairs. Such compounds are not limited to the following, but can be exemplified by: compounds having an amine structure represented by formula (3) below, compounds having an imine structure represented by formula (4) below, compounds having a phosphine structure represented by formula (5) below, and onium salts derived from them. The structures represented by formulas (3) to (5) below may be contained in multiples in the compound of component (B), and when multiples are contained, they may be the same or different.

[0067] [Chemical 8]

[0068] In formula (3), the ・・ on the nitrogen atom represents a non-shared electron pair.

[0069] [Chemical 9] In formula (4), the ・・ on the nitrogen atom represents a non-shared electron pair.

[0071] [Chemical 10]

[0072] In formula (5), the ・・ on the phosphorus atom represents a non-shared electron pair.

[0073] The compound having the amine structure represented by the above formula (3) is not limited to the following, for example: amine compounds such as aliphatic amines, heterocyclic amines, aromatic amines, or acehydrazine compounds.

[0074] Aliphatic amines are compounds in which an amino group or a substituted amino group is bonded to a hydrocarbon that does not have an aromatic ring. Compounds having the structure represented by formula (3) above are not limited to the following, but may include, for example: methylamine, ethylamine, diethylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, allylamine, tri(2-aminoethyl)amine, tri[2-(dimethylamino)ethyl]amine, ethylenediamine, cyclohexanediamine, tetramethylethylenediamine, 1,6-bis(dimethylamino)hexane, 1,3-bis(dimethylamino)propane, diethyltriamine, triethyltetramine, hexamethylenetetramine, tetraethylpentamine, dimethylaminopropylamine, pentamethyldiethyltriamine 2-Dimethylaminoethanol, m-phenylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, tris(hydroxymethyl)aminomethane, N,N-diisopropylethylamine, 1,8-bis(dimethylamino)naphthalene, 1,4-diazabicyclo[2.2.2]oct-2-ylmethanol, isoflavone diamine, 1,3-diaminomethylcyclohexane, 1,4-diaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norethene diamine, 1,2-diaminocyclohexane, dimethylbenzylamine, 2,4,6-tris(dimethylaminomethyl)phenol, polyetheramine, etc.

[0075] Heterocyclic amines are cyclic compounds in which the heteroatom constituting the heterocycle is nitrogen. As for compounds having the structure represented by the above formula (3) as heterocyclic amines, they are not limited to the following, for example: pyrrolidine, pyrrole, piperidine, piperazine, carbazole, triethylenediamine, pyridine, imidazoidine, pyrazolidine, thiazoidine, thiozoline, thiazoline, triazacyclohexane, and compounds having substituents.

[0076] Aromatic amines are compounds in which an amino group or a substituted amino group is bonded to an aromatic ring. As for compounds having the structure represented by formula (3) above as aromatic amines, they are not limited to the following, but may include, for example: diaminodiphenylmethane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3'-diethyl- 4,4'-Diaminodiphenylmethane, 3,5,3',5'-Tetramethyl-4,4'-Diaminodiphenylmethane, 4,4'-Methylenebis[N-(1-methylpropyl)aniline], Trimethylenebis(4-aminobenzoate), Poly-1,4-Butanediol bis(p-aminobenzoate), Diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, Dimethylthiotoluenediamine, 1,2-bis(phenylamino)ethane, Aminobenzylamine, etc.

[0077] Azuridine compounds are compounds in which an amino group is formed on the nitrogen bond constituting the amide group. They are not limited to the following, but may include, for example: diazuridine succinate, diazuridine adipic acid, diazuridine sebacate, diazuridine phthalate, diazuridine isophthalate, diazuridine terephthalate, diazuridine dodecanoic acid, diazuridine p-hydroxybenzoate, diazuridine salicylate, diazuridine phenylaminopropionate, diazuridine maleate, etc.

[0078] The compounds having the imine structure represented by the above formula (4) are not limited to the following, for example: imine compounds, heterocyclic amines. Imine compounds are compounds having nitrogen-carbon double bonds, which are usually obtained by reacting amine compounds with aldehyde compounds or ketone compounds. As for the compounds represented by the above formula (4) as imine compounds, they are not limited to the following, for example: diphenylmethane imine, N,N'-(ethane-1,2-dimethylene)bis(2,4,6-trimethylaniline), N,N'-bis(thylene)ethylenediamine, N-thyleneaniline, N,N'-bis(thylene)-1,2-propanediamine, N,N'-bis(thylene)-1,2-phenylenediamine, etc. As for the compounds represented by the above formula (4) as heterocyclic amines, they are not limited to the following, for example: pyridine, pyridine, pyrimidine, pyridine, diazole, diazole, thiadiazole, dithiazolium, triazole, etc., and compounds having substituents thereon.

[0079] Furthermore, by reacting ammonia, an ammonium salt containing ammonia and an inorganic or organic acid, or an amine compound with a dialdehyde compound or a diketone compound, an imine compound can also be obtained as an oligomer or polymer having an imine bond. The dialdehyde compound or diketone compound that forms an oligomer or polymer as an imine compound is not limited to the following, but examples include: glyoxal, methylglyoxal, 2,3-butanedione, 2,3-pentanedione, 2,3-heptanedione, 3,4-hexanedione, 5-methyl-2,3-hexanedione, etc. The ammonium salt containing ammonia and an inorganic or organic acid is not limited to the following, but examples include: ammonium chloride, ammonium carbonate, ammonium acetate, ammonium sulfite, ammonium nitrite, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium oxalate, etc. As an amine compound, it is not limited to the following, but may include: aliphatic amines or aromatic amines, or 2-(amino(hydroxy)methyl)phenol, 2-amino-2-hydroxyacetaldehyde, 1,2-diaminoethane-1,2-diol, etc., which are specific examples of the above-mentioned component (B).

[0080] The compound containing component (B) of the structure represented by the above formulas (3) and (4) is not limited to the following, for example, heterocyclic amines or guanidine compounds.

[0081] As for compounds containing component (B) of the structures represented by formulas (3) and (4) above as heterocyclic amines, they are not limited to the following, for example: 4-dimethylaminopyridine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo(5,4,0)-undecene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 9-pyrrolidine, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene and other heterocyclic amines, or imidazoline compounds such as 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-(2-hydroxyphenyl)imidazoline, 2-ethyl-4-methylimidazoline and other imidazoline compounds. Heterocyclic amines may further be aromatic, that is, aromatic heterocyclic amines. Examples of aromatic heterocyclic amines containing the structures represented by formulas (3) and (4) above include: imidazole, pyrazole, succinate, thiazole, triazole, tetraazole and other heterocyclic aromatic amines with an azole skeleton, as well as compounds with substituents.

[0082] Guanidine compounds are compounds having a structure in which two amino groups are bonded to the carbon atom constituting the carbon-nitrogen double bond. As for compounds containing the structures represented by formulas (3) and (4) above, they are not limited to the following, but can be exemplified by: guanidine salts such as guanidine nitrate, guanidine carbonate, guanidine phosphate, guanidine aminosulfonate, and aminoguanidine bicarbonate; methyl guanidine; ethyl guanidine; propyl guanidine; butyl guanidine; dimethyl guanidine; trimethyl guanidine; tetramethyl guanidine; pentamethyl guanidine; cyclohexyl guanidine; phenyl guanidine; diphenyl guanidine; toluenemethyl guanidine; acetyl guanidine; diacetyl guanidine; propionyl guanidine; dipropionyl guanidine; cyanoacetyl guanidine; guanidine succinate; diethylcyanoacetyl guanidine; and dicyanodiamidine. N-oxymethyl-N'-cyanoguanidine, N,N'-dicarbonethoxyguanidine, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, 2-cyanoguanidine, 2-cyanoguanidine-aniline adduct, 2-cyanoguanidine-methylaniline adduct, 2-cyanoguanidine-diaminodiphenylmethane adduct, 2-cyanoguanidine-diaminodiphenyl ether adduct, etc.

[0083] As a compound having the phosphine structure represented by the above formula (5), examples of phosphine compounds can be given. The phosphine compound is not limited to the following, but examples include: tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine, and other aliphatic phosphines; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2,6 ... Aromatic phosphines such as tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphine)ethane, 1,3-bis(diphenylphosphine)propane, 1,4-bis(diphenylphosphine)butane, 1,2-bis(diphenylphosphine)acetylene, and 2,2'-bis(diphenylphosphine)diphenyl ether; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; and aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants.

[0084] As for onium salts derived from the compounds represented by formulas (3) to (5) above, examples include phosphonium salts, ammonium salts, etc.

[0085] As a phosphonium salt, it is not limited to the following, but may include, for example: tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitictate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate, etc., aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, etc. Aromatic phosphonium salts such as phosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetrap-tolylborate, tetraphenylphosphonium tetrap-tolylborate, tetraphenylphosphonium tetrap-tolylborate, triphenylethylphosphonium tetraphenylborate, tri(3-methylphenyl)ethylphosphonium tetraphenylborate, tri(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium isothiocyanate, tetraphenylphosphonium isothiocyanate, and butyltriphenylphosphonium isothiocyanate.

[0086] As an ammonium salt, it is not limited to the following, for example: benzyltrimethylammonium chloride, tetramethylammonium p-toluenesulfonate, succinylcholine chloride, 3-(trifluoromethyl)phenyltrimethylammonium iodide, tetramethylammonium hydrogen sulfate, benzyltrimethylammonium hydroxide, benzyltrimethylammonium chloride, 2-hydroxyethyltrimethylammonium hydroxide, 2-hydroxyethyltrimethylammonium chloride, hexadecyltrimethylammonium hydroxide, hexadecyltrimethylammonium chloride, tetraethylammonium hydroxide, tetraethylammonium chloride, tetrapropylammonium hydroxide, tetrapropylammonium chloride, tetrabutylammonium hydroxide, tetrabutylammonium chloride, tetrahexylammonium hydroxide, tetrahexylammonium chloride, trimethylphenylammonium chloride, etc.

[0087] The molecular weight of the compound having the structure of component (B) of the above formulas (3) to (5) is not limited to the following, but from the viewpoint of maintaining good compatibility with the specified resin, it is preferably 50,000 or less, more preferably 40,000 or less, further preferably 30,000 or less, further preferably 20,000 or less, even more preferably 10,000 or less, and especially preferably 5,000 or less. The lower limit of the molecular weight of component (B) is not limited to the following, but from the viewpoint of non-volatileness, it is preferably 10 or more, more preferably 20 or more, further preferably 30 or more, further preferably 40 or more, and even more preferably 50 or more. If the molecular weight is, for example, about 500 or less, it can be determined by mass spectrometry, and if it is 500 or more, it can be determined as the weight average molecular weight by gel permeation chromatography (GPC). In LC-MS and GC-MS, the molecular weight can be calculated from the molecular ion peak of the obtained mass spectrum. Furthermore, in the case of GPC, specifically, the HLC-8320GPC manufactured by Tosoh can be used as the measuring device, the Shodex KF-804 / KF-803 / KF-802 / KF-802 manufactured by RESONAC can be used as the column, tetrahydrofuran or the like can be used as the mobile phase, the measurement can be performed at a column temperature of 40°C, and the weight-average molecular weight of polystyrene can be calculated using the calibration curve of standard polystyrene.

[0088] The compound as component (B) has the structure of the above formulas (3) to (5), fully demonstrating the function of hydrogen bond acceptor, and in view of taking into account the preservation of stability, the pKa of the conjugate acid is preferably 1.5 or more and 13 or less, more preferably 2 or more and 12 or less, and even more preferably 2.5 or more and 10 or less.

[0089] As described above, from the viewpoint of more easily imparting low-temperature curing properties, component (B) is preferably a compound having the structure of the above formula (3) and / or formula (4), more preferably a compound containing the structure of the above formula (3) and formula (4). From the viewpoint of obtaining good adhesion strength of the adhesive, rust inhibitor, resin composition and hardened material to the substrate in the following embodiments, it is even more preferably a heterocyclic amine containing the structure of the above formula (3) and formula (4), more preferably an aromatic heterocyclic amine containing the structure of the above formula (3) and formula (4), and even more preferably an aromatic heterocyclic amine containing two or more nitrogen atoms, especially a compound containing triazole and / or imidazole.

[0090] The triazole compound preferably used as component (B) above is not limited to the following, but may include, for example: 1,2,4-triazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 1-bis(2-ethylhexyl)aminomethyl-1,2,4-triazole, 2-hydroxy-1,2,4-triazole- 3-Benzobenzoic acid, 3-amino-5-mercapto-1,2,4-triazole, 5-amino-1,2,4-triazole-3-carboxylic acid, 3,5-diphenyl-1,2,4-triazole, benzotriazole, 4-carboxybenzotriazole, 5-carboxybenzotriazole, 1-(1',2'-dicarboxyethyl)benzotriazole, 1-(2,3-dicarboxypropyl)benzotriazole, 5-methylbenzotriazole, etc.

[0091] Furthermore, the imidazole compound preferably used as component (B) is not limited to the following, but may include, for example: imidazole, 2-methylimidazole, 2-ethylimidazole, 4-methylimidazole, 2-undecylimidazole, 2-heptadecanylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-5-methylimidazole, 4-butyl-5-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl 2-Methylimidazole, 1-benzyl-2-phenylimidazole, 2,2'-biimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole ontyl trimellitate, 1-cyanoethyl-2-phenylimidazole ontyl trimellitate, 2,4-diamino-6-[2'-methylimidazole-(1')]-ethyl-symmetric Tris(2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-symmetric tris(2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-symmetric tris(2,4-diamino-6-[2 ...isocyanate adduct, 2-phenylimidazolylisocyanate adduct, 2-phenyl-4,5-dihydroxymethylimidazolyl, 2-phenyl-4-methyl-5- Hydroxymethyl imidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, etc., among which imidazole, 4-methylimidazolium, 2-ethyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 4-ethyl-5-methylimidazolium, 4-butyl-5-methylimidazolium, and 2,2'-biimidazole are preferred from the viewpoint of curing properties in low-temperature regions and adhesion to the substrate.

[0092] As a mechanism by which the composition of this embodiment contains component (B) relative to component (A) to exhibit hardening properties in a low-temperature region below 150°C, the following is considered, but not intended to be limited to: Component (A) suppresses the nucleophilicity of the nitrogen moiety through intramolecular hydrogen bonds, and thus exists in a state of decreased reactivity. Normally, to harden it, it is necessary to heat it until the hydrogen bonds weaken and sufficient reactivity is generated, thus requiring a high temperature of about 150°C or higher. In contrast, if component (B) coexists, since component (B) is a compound that functions as a hydrogen bond acceptor, intermolecular hydrogen bonds can be formed between component (A) and component (B), or the hydrogen bonds of component (A) can be weakened. In this way, the restriction of the nucleophilicity of component (A) is weakened, reactivity is increased, and the effect of exhibiting hardening properties in a low-temperature region is obtained, so that sufficient hardening properties can be exhibited even in a low-temperature region below about 150°C.

[0093] Furthermore, component (B) does not require stoichiometry relative to component (A). This mechanism is considered as follows, but is not intended to be limited to the following. As part of the intermolecular hydrogen bonds between component (A) and component (B), the intramolecular hydrogen bonds weaken, thus reacting first with curing resin components such as epoxy resin. This generates anions within the system, thereby causing proton donation from other components (A) that have not participated in intermolecular hydrogen bonds. The intramolecular hydrogen bonds of the donating component (A) weaken, thus exhibiting reactivity, and a chain reaction occurs. Therefore, component (B) functions as a reaction initiator, and can fully exert its function even in small amounts relative to component (A).

[0094] Furthermore, especially when component (B) is an aromatic heterocyclic amine, the non-shared electron pairs of component (B) are stabilized by their aromaticity rather than localization, thus making it less likely to react excessively with the curing resin components, and exhibiting excellent stability. Moreover, due to its aromaticity, it is easy to detach, thereby breaking the hydrogen bonds with component (A) and forming hydrogen bonds with other components (A), thus easily exerting its catalytic function, and exhibiting a tendency to obtain effects with a smaller amount.

[0095] Regarding the content of component (B), from the viewpoint of fully obtaining the reaction-promoting effect of component (A) produced by component (B) relative to the total mass of components (A) and (B), it is preferably 50 ppm or more, more preferably 100 ppm or more, further preferably 150 ppm or more, and further preferably 200 ppm or more. On the other hand, as an upper limit, from the viewpoint of the adhesion of the resin composition using the composition of this embodiment to various substrates, such as metals, it is preferably less than 10,000 ppm, more preferably 9,000 ppm or less, further preferably 8,000 ppm or less, further preferably 7,000 ppm or less, and further preferably 6,000 ppm or less. By keeping the content of component (B) within the above-mentioned value range, a resin composition that maintains storage stability and also takes into account adhesion in addition to curing properties in low-temperature regions is obtained.

[0096] As a mechanism by which the composition of this embodiment contains a small amount of component (B), thereby improving the adhesion of the resin composition containing the composition of this embodiment to substrates, such as metals, the following considerations are made, but are not intended to be limited to the following. If it is component (A) alone, the nitrogen portion participating in intramolecular hydrogen bonding and the phenolic hydroxyl group form an intramolecularly closed structure, thus reducing the efficiency of forming coordinate bonds or hydrogen bonds with metal atoms, metal oxides, or hydroxyl groups present on the surface of the substrate. In contrast, if component (B) is present, it does not form intermolecular hydrogen bonds with component (A), weakening the hydrogen bonding of component (A). Therefore, the nitrogen portion of component (A), which could not previously interact with the substrate, can now participate in hydrogen bonds or coordinate bonds with the substrate, thus improving adhesion. On the other hand, if component (B) is more abundant, component (B) itself also acts on the surface of the substrate, making it difficult for component (A) to align on the surface of the substrate, thus sometimes reducing adhesion.

[0097] (Method for manufacturing the composition) The composition of this embodiment is obtained by adding component (B) to the above-mentioned component (A) and mixing. The mixing method is not particularly limited, and methods known to the industry can be used. It is not limited to the following; for example, it can be obtained by thoroughly mixing to homogeneity using a melt mixer, a mixing roller such as a three-roll mill, a dispersing mixer, a planetary mixer, a rotary mixer, a kneader, an extruder, a powder mixer, etc. Furthermore, the component that becomes component (B) can also be added during the process of obtaining component (A) or generated in the system. In this case, the effort of separately mixing component (A) and component (B) is saved, which is therefore preferable.

[0098] (Uses of the Composition) The composition of this embodiment can be used as a component of a hardener, adhesion promoter, or rust inhibitor. That is, the hardener, adhesion promoter, and rust inhibitor of this embodiment each contain the composition of this embodiment. The composition of this embodiment has excellent storage stability and can produce a resin curing reaction from a low temperature range, thus it can be used as a good hardener. Furthermore, the composition of this embodiment reacts well with various substrates, such as metals, thus it can be used as a constituent material of adhesion promoters or rust inhibitors, for example, by adding it to a specified resin, a resin composition with excellent adhesion and rust prevention effect can be obtained.

[0099] (Additives) The composition of this embodiment may, as needed, contain stabilizers or the like as additives in addition to the above-mentioned components (A) and (B).

[0100] As a stabilizer, for example, to improve the storage stability of the resin composition, boric acid and cyclic borate esters, isocyanuric acid, barbituric acid, aluminum chelating agents, etc., are preferred, but not particularly limited to them. Cyclic borate esters refer to those containing boron in a cyclic structure. From the viewpoint of resin compatibility and curing uniformity, cyclic borate esters are preferably 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaboranecyclohexane). Furthermore, a stabilizer may be used alone or in combination with two or more.

[0101] There are no special restrictions on the amount of the above additives. As long as you are a business operator, you can set the appropriate amount of additives according to the desired performance.

[0102] [Resin Composition] The resin composition of this embodiment contains the composition of this embodiment described above and a curing resin. The resin composition of this embodiment is obtained by mixing the curing resin into the composition of this embodiment described above. There are no particular limitations on the mixing method, and methods known to the industry can be used. It is not limited to the following, for example, it can be obtained by thoroughly mixing until uniform using a melt mixer, a mixing roller such as a three-roll mill, a dispersing mixer, a planetary mixer, a rotary mixer, a kneader, an extruder, a powder mixer, etc.

[0103] (Curing Resin) The curing resin is any resin having a functional group that can react with imidazole compounds, and is not limited to the following, such as epoxy resin, epoxidized resin, etc. One or more of them may be used.

[0104] Epoxy resins are those having an average of one or more epoxy groups within their molecules. Examples of epoxy resins include, but are not limited to, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol E type epoxy resins, bisphenol AD ​​type epoxy resins, bisphenol AF type epoxy resins, tetrabromobisphenol A type epoxy resins, biphenyl type epoxy resins, bixylenol type epoxy resins, tetrabromobiphenyl type epoxy resins, diphenyl ether type epoxy resins, benzophenone type epoxy resins, phenyl benzoate type epoxy resins, and diphenyl sulfide type epoxy resins. Bifunctional epoxy resins include: epoxy resins, diphenyl sulfide epoxy resins, diphenyl disulfide epoxy resins, naphthalene epoxy resins, anthracene epoxy resins, hydroquinone epoxy resins, methyl hydroquinone epoxy resins, butyl hydroquinone epoxy resins, resorcinol epoxy resins, methyl resorcinol epoxy resins, catechol epoxy resins, and N,N-diglycidyl aniline epoxy resins.

[0105] Also, examples include: N,N-diglycidylaminobenzene type epoxy resin, o-(N,N-diglycidylamino)toluene type epoxy resin, tris(N,N-diglycidylamino)toluene type epoxy resin, tris(N,N-diglycidylamino)toluene type epoxy resin, etc., which are trifunctional epoxy resins.

[0106] Examples include: naphthalene-type tetrafunctional epoxy resin, tetraglycidyl diaminodiphenylmethane-type epoxy resin, diaminobenzene-type epoxy resin, and other tetrafunctional epoxy resins.

[0107] Further examples include: phenolic varnish epoxy resin, cresol varnish epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, dicyclopentadiene epoxy resin, naphthol aralkyl epoxy resin, brominated phenolic varnish epoxy resin, and other multifunctional epoxy resins.

[0108] Further examples include: (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane-type diglycidyl ether, dicyclopentadiene-type diglycidyl ether, and similar epoxy resins.

[0109] Other examples include tri-hydroxymethylpropane triglycidyl ether, glycerol triglycidyl ether, and other tri-epoxy resins.

[0110] Examples include alicyclic epoxy resins such as vinyl dioxide (3,4-cyclohexene) and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dialkyl.

[0111] Further examples include glycidylamine type epoxy resins such as tetraglycidylbis(aminomethyl)cyclohexane.

[0112] Further examples include: hydantoin-type epoxy resins such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin; and epoxy resins having a polysiloxane backbone such as 1,3-bis(3-glycidyloxypropyl)-1,1,3,3-tetramethyldisiloxane.

[0113] Examples include: 2-ethylhexyl glycidyl ether, cyclohexanediethanol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, hydrogenated bisphenol A type epoxy resin, polysiloxane modified epoxy resin, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether. Oil ethers, glycerol diglycidyl ethers, neopentyl glycol diglycidyl ethers, cyclohexane-type diglycidyl ethers, dicyclopentadiene-type diglycidyl ethers, trimethylolpropane triglycidyl ethers, glycerol triglycidyl ethers, vinyl dioxide (3,4-cyclohexene), 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dimethylalkanes, tetraglycidyl bis(aminomethyl)cyclohexane and other glycidylamine epoxy resins, 1, 3-Diglycidyl-5-methyl-5-ethylhydantoin type epoxy resin, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane type epoxy resin, phenyl glycidyl ether, tolyl glycidyl ether, p-butylphenyl glycidyl ether, epoxy phenyl ethane, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidylphthalimide, Butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α-pinene oxide, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methylepoxyethyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, and neodecanoic acid glycidyl ester are also aliphatic epoxy resins and alicyclic epoxy resins that can be used as reactive diluents.

[0114] The above-mentioned epoxy resins may be used in combination of one or more.

[0115] Cyclosulfide resins are those that have an average of one or more cyclosulfide groups in their molecules. Cyclosulfide resins are not limited to the following, but may include, for example: bisphenol-type cyclosulfide resins formed by thioglycidylating bisphenols such as bisphenol A, bisphenol F, bisphenol E, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, and tetrabromobisphenol A; hydrogenated bisphenol-type cyclosulfide resins formed by thioglycidylating hydrides of bisphenols such as bisphenol A, bisphenol F, bisphenol E, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, and tetrabromobisphenol A; and cyclosulfide resins formed by thioglycidylating biphenols, dihydroxynaphthalene, dihydroxyanthracene, and 9,9-bis(4-hydroxyphenyl)... Cyclosulfide resins formed by thioglycidylating other diphenols such as phenyl ether; cyclosulfide resins formed by thioglycidylating triphenols such as 1,1,1-tris(4-hydroxyphenyl)methane and 4,4-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylene)bisphenol; cyclosulfide resins formed by thioglycidylating tetraphenols such as 1,1,2,2-tetra(4-hydroxyphenyl)ethane; phenolic varnish-type cyclosulfide resins formed by thioglycidylating phenolic varnishes, cresol phenolic varnishes, bisphenol A phenolic varnishes, brominated phenolic varnishes, and brominated bisphenol A phenolic varnishes; and cyclosulfide resins formed by thioglycidylating glycerol or... Aliphatic ether-type cyclic sulfur resins formed by thioglycidylating polyols such as polyethylene glycol; ether ester-type cyclic sulfur resins formed by thioglycidylating hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthylcarboxylic acid; ester-type cyclic sulfur resins formed by thioglycidylating polycarboxylic acids such as phthalic acid and terephthalic acid; thioglycidylated compounds of amine compounds such as 4,4-diaminodiphenylmethane or m-aminophenol, or amine-type cyclic sulfur resins such as triglycidyl cyanurate; thioglycidylated compounds of polyalkylene polyamines such as diethyltriamine or triethyltetraamine and polyamide polyamines such as adipic acid; and 3',4'-cyclothiocyclohexane... Alicyclic cyclosulfides such as methyl 3,4-cyclothiocyclohexyl alkylcarboxylate, bis(3,4-cyclothiocyclohexyl) adipic acid, and 1,2-cyclothio-4-vinylcyclohexane; polysiloxane-modified cyclosulfide resins obtained by reacting organopolysiloxanes with cyclosulfide resins or phenolic varnish-type cyclosulfide resins; thioglycidyl methacrylate or methyl 3,4-cyclothiocyclohexyl methacrylate; cyclothiopropane, cyclohexyl sulfide, and other cyclosulfide compounds and their polymers; bis(2,3-cyclothiopropyl) sulfide or bis(2,3-cyclothiopropylthio)ethane; bis(5,6-cyclothio-3-thiohexane) sulfide, etc. These compounds may be used individually or in combination of two or more.

[0116] As a curing resin, it is preferable to contain epoxy resin in terms of availability and the tendency for the cured product to exhibit excellent reliability and insulation properties. More preferably, it is an epoxy resin that is liquid at 25°C. By containing an epoxy resin that is liquid at 25°C, there is a tendency for components (A) and (B) to be uniformly dissolved or dispersed in the curing resin, resulting in a cured product with superior strength or heat resistance.

[0117] The content of components (A) and (B) in the resin composition of this embodiment is not particularly limited. The total amount of components (A) and (B) relative to 100 parts by weight of the curing resin is preferably 0.1 to 50 parts by weight, more preferably 0.2 to 45 parts by weight, and even more preferably 0.3 to 40 parts by weight. Within this range, there is a tendency to obtain sufficient curability, and the resulting cured product tends to have excellent strength or heat resistance.

[0118] (Other components) The resin composition of this embodiment may further contain other hardeners, other resins, fillers, silane coupling agents, diluents, pigments, dyes, flow modifiers, tackifiers, reinforcing agents, release agents, wetting agents, flame retardants, surfactants, stabilizers, etc., as needed.

[0119] <Other Curing Agents> Other curing agents may be widely used as long as they are previously known curing agents for curable resins such as epoxy resins, and are not limited to the following, for example: phenolic curing agents, acid anhydride curing agents, reactive ester curing agents, cyanate ester curing agents, carbodiimide curing agents, benzo[a]pyrene curing agents, thiol curing agents, catalyst-type curing agents, etc. One of these may be used alone, or two or more may be used in combination.

[0120] As a phenolic curing agent, it is not limited to the following, but may include, for example: phenolic varnish resin, bisphenol A phenolic varnish resin, cresol phenolic varnish resin, phenol aralkyl resin, cresol aralkyl resin, naphthol-phenol co-condensed phenolic varnish resin, naphthol-cresol co-condensed phenolic varnish resin, allyl propylene phenolic resin, phenolic resin containing a dicyclopentadiene skeleton, phenolic resin containing a biphenyl skeleton, phenolic resin containing a naphthyl skeleton, and phenolic resin containing a trihalomethane skeleton, etc. Furthermore, the term "phenolic resin containing a trihalomethane skeleton" refers to a resin that functions as a curing agent for epoxy resins, possessing both a trihalomethane skeleton and a structure derived from phenolic compounds within a single molecule. It is typically manufactured by the condensation of phenolic compounds with compounds containing trihalomethane rings, such as melamine and benzoguanamine, and formaldehyde. Among these, from the viewpoint of improving the strength of the hardened material, it is preferable to use phenolic hardeners containing bisphenol A type structure, bisphenol F type structure, bisphenol AF type structure, naphthalene structure, phenolic varnish structure, cyclohexane structure, cyclohexanediol structure, butadiene structure, biphenyl type structure, bixylenol structure, cresol varnish structure, dicyclopentadiene structure, triphenol structure, naphthol structure, naphthyl ether structure, anthracene structure, tetraphenylethane structure, bisphenol acetophenone structure, fusiform structure, and triphenylene structure.

[0121] Commercially available phenolic hardeners are not limited to the following, but may include: Trade names manufactured by DIC Corporation: TD2090 (phenolic resin), EXB-9500 (phenolic resin containing naphthalene skeleton), LA3018, LA3018-50P, LA7052, LA7054, LA1356 (phenolic resin containing triphenylene skeleton); trade names manufactured by UBE Corporation: HF-1M (phenolic resin), MEH-7700, MEH-7810, MEH-7851 (phenolic resin containing biphenyl skeleton); trade names manufactured by Nippon Chemical Co., Ltd.: NHN, CBN, GPH (phenolic resin containing naphthalene skeleton); Nippon Steel Chemical &... Material Company manufactures products under the following names: SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (phenolic resin containing naphthalene skeleton), etc.

[0122] As an acid anhydride-based curing agent, it is not limited to the following, for example: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl terephthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.

[0123] The term "active ester-based curing agent" refers to a compound that functions as a curing agent for epoxy resins and contains active esters in its molecule. As an active ester-based curing agent, it is not limited to the following, but from the viewpoint of ensuring crosslinking density, it is preferably a compound having two or more active ester groups in one molecule. Furthermore, from the viewpoint of the heat resistance or strength of the obtained cured product, it is more preferably an active ester compound obtained by reacting a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound; more preferably, it is an active ester compound obtained by reacting a carboxylic acid compound with one or more of a compound selected from phenol, naphthol, and thiol compounds. Furthermore, it is even more preferably an aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having phenolic hydroxyl groups. Furthermore, it is even more preferable that the aromatic compound is obtained by reacting a compound having at least two carboxylic acids per molecule with an aromatic compound having phenolic hydroxyl groups, and that each molecule of the aromatic compound has at least two active ester groups. The active ester curing agent can be linear or multi-branched. Furthermore, if the compound having at least two carboxylic acids per molecule is a compound containing an aliphatic chain, its compatibility with epoxy resin can be improved; if it is a compound having an aromatic ring, the resin composition of this embodiment tends to further improve strength or heat resistance.

[0124] Here, examples of the carboxylic acid compounds used to form the above-mentioned active ester-based curing agent include: benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are particularly preferred, and isophthalic acid and terephthalic acid are even more preferred. Examples of the thiocarboxylic acid compounds used to form the above-mentioned active ester-based curing agent include: thioacetic acid and thiobenzoic acid, but they are not particularly limited to these.

[0125] The phenol or naphthol compound used to form the above-mentioned active ester-based curing agent is not limited to the following, and examples include: hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyroglucinol, dicyclopentadienyldiol, phenolic varnish, etc. Among these, from the viewpoint of resin solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyroglucinol, dicyclopentadienyl diol, phenolic varnish, and more preferably catechol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, and trihydroxybenzophenone. The varnish comprises hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyroglucinol, dicyclopentadienyldiol, and phenolic varnish, and more preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiol, and phenolic varnish, and more preferably dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyldiol, and phenolic varnish, and even more preferably dicyclopentadienyldiol and phenolic varnish, and especially preferably dicyclopentadienyldiol.

[0126] The thiol compound used to form the above-mentioned active ester-based hardener is not limited to the following, for example: benzene dithiol, tridithiol, etc.

[0127] Furthermore, the active ester compound used as an active ester-based hardener is not limited to the following, for example, the active ester compounds disclosed in Japanese Patent Application Publication No. 2004-277460 and Japanese Patent Application Publication No. 2013-40270 may be used, as well as commercially available active ester compounds. Commercially available active ester compounds are not limited to the following, but may include: DIC Corporation's trade names: EXB9451, EXB9460, EXB9460S, HPC-8000-65T (active ester compounds containing dicyclopentadiene-type diphenol structures), EXB9416-70BK (active ester compounds containing naphthalene structures), EXB9050L-62M (active ester compounds containing phosphorus atoms), and Mitsubishi Chemical Corporation's trade names: DC808 (active ester compounds containing acetylated compounds of phenolic varnish), YLH1026 (active ester compounds containing benzoyl compounds of phenolic varnish), etc.

[0128] The term "cyanate ester curing agent" refers to a curing agent for epoxy resin that contains a cyanate group in its molecule. Cyanate ester curing agents are not limited to the following, but may include, for example: phenolic varnish type (phenolic varnish type, alkylphenolic varnish type, etc.) cyanate ester resins, dicyclopentadiene type cyanate ester resins, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate ester resins, and some triterpenoid prepolymers thereof. The cyanate resin is not limited to the following, but may include, for example: bisphenol A dicyanate, polyphenol cyanates (oligomeric (3-methylene-1,5-phenyl cyanate), 4,4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate-phenyl)propane, 1,1-bis(4-cyanate-phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate-phenyl-1-(methylethylidene))benzene, bis(4-cyanate-phenyl) sulfide, bis(4-cyanate-phenyl) ether and other difunctional cyanate resins, self-phenolic varnish, cresolic varnish, polyfunctional cyanate resins derived from phenolic resins containing a dicyclopentadiene structure, and some triterpenoid prepolymers of such cyanate resins, etc. They can be used in one or more combinations. Commercially available cyanate ester resins are not limited to the following, for example, such as: CYTESTER (registered trademark) TA (bisphenol A type cyanate ester resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0129] As a carbodiimide-based curing agent, it is not limited to the following, for example: trade names manufactured by Nisshinbo Chemical: Carbodilite V-02B, V-03, V-04K, V-07, V-09, and trade names manufactured by Rhein Chemie: Stabaxol P, P400, Hycasyl 510, etc.

[0130] As a benzo[a]-type curing agent, it is not limited to the following, for example: HFB2006M manufactured by Showa Polymer Co., Ltd., and Pd, Fa, ALP-d manufactured by SHIKOKU KASEI HOLDINGS Co., Ltd.

[0131] As a thiol-based curing agent, it is acceptable as long as it contains two or more thiol groups in one molecule, and is not limited to the following, for example: 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolic acid ester), pentaerythritol tetra(thioglycolic acid ester), ethylene glycol dithioglycolic acid ester, 1,4-bis(3-mercaptobutoxy)butane, tris[(3-mercaptopropoxy)-ethyl]isocyanurate, 1,3,5-tris( 3-Mercaptobutoxyethyl)-1,3,5-tris(2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptopropionate), 1,3,4,6-tetra(2-mercaptoethyl)glycourea, 4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc.

[0132] As a catalyst-type curing agent, it is not limited to the following, for example, cationic thermosetting catalysts, etc.

[0133] <Other Resins> The resin composition of this embodiment may further contain other resins. By containing other resins, cracking or breakage can be prevented and the shape can be maintained when molding the resin composition.

[0134] Other resins are not limited to the following, but may include, for example: phenoxy resins, polyvinyl acetal resins, ethylene resins containing anhydride groups, polyolefin resins, polybutadiene resins, polyimide resins, polyamide-imide resins, styrene-based elastomer resins, polyether resins, polyphenylene ether resins, polyether resins, and acrylic resins. These may be used alone or in combination of two or more.

[0135] As a phenoxy resin, for example, a phenoxy resin having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic varnish skeleton, biphenyl skeleton, fumonisin skeleton, dicyclopentadiene skeleton, norethene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton and trimethylcyclohexane skeleton may be used. The terminal of the phenoxy resin may be any functional group such as phenolic hydroxyl group or epoxy group. As for phenoxy resins, they are not limited to the following, but can be exemplified by: Mitsubishi Chemical's trade names: 1256, 4250 (phenoxy resins containing a bisphenol A backbone), YX8100 (phenoxy resins containing a bisphenol S backbone), YX6954, YX6954BH30 (phenoxy resins containing a bisphenol acetophenone backbone), YX7553, YX7553BH30 (phenoxy resins containing a biscresol genistein backbone), YL6794 (phenoxy resins containing a terpene backbone), YL7213, YL7290 (phenoxy resins containing a trimethylcyclohexane backbone), YL7500BH30, YL7769BH30, YL7482; and Nippon Steel Chemical & Material's trade names: FX280, FX293 (phenoxy resins containing a bisphenol genistein backbone), etc.

[0136] The polyvinyl acetal resin is not limited to the following, for example: the trade names of Electrochemical Industry Co., Ltd.: Denka Butyral 4000-2, 5000-A, 6000-C, 6000-EP; the trade names of Sekisui Chemical Industry Co., Ltd.: S-LEC BH series, BX series, KS series (e.g. KS-1), BL series, BM series, etc.

[0137] The ethylene resin containing an anhydride group is not limited to the following, for example, it can be obtained by copolymerizing the monomer (d1) containing an anhydride group with other monomers (d2). The monomer (d1) containing an anhydride group is not particularly limited, for example: maleic anhydride, iconic anhydride, citrate anhydride, aconitic anhydride. The other monomer (d2) is not particularly limited as long as it can copolymerize with the monomer (d1) containing an anhydride group, for example, vinyl unsaturated monomers such as (meth)acrylic acid, (meth)acrylate, and styrene can be used. The ethylene resin containing anhydride group is not limited to the following, for example: trade names manufactured by Cray Valley: EF-30, EF-40, EF-60, EF-80.

[0138] The polyolefin resin is not limited to the following, but may include, for example: polyethylene, polypropylene, polyvinyl chloride, etc. The polybutadiene resin is not limited to the following, but may include, for example: trade names manufactured by Nippon Soda: G-1000, G-3000, GI-1000, GI-3000; trade name manufactured by Idemitsu Petrochemical Co., Ltd.: R-45EPI; trade name manufactured by Daicel Co., Ltd.: Epofriend AT501; trade name manufactured by Cray Valley Co., Ltd.: Ricon130, Ricon142, Ricon150, Ricon657, Ricon130MA, etc.

[0139] The polyimide resin is not limited to the following, for example: RIKACOAT SN-20 and PN-20 manufactured by Shin Nippon Rika Co., Ltd., and UNIDIC V-8000 manufactured by DIC Co., Ltd. Specific examples of polyimide resins include: linear polyimides obtained by reacting difunctional hydroxyl-terminated polybutadiene, diisocyanate compounds and tetrabasic anhydrides (Japanese Patent Application Laid-Open No. 2006-37083), and modified polyimides containing a polysiloxane backbone (Japanese Patent Application Laid-Open No. 2002-12667, Japanese Patent Application Laid-Open No. 2000-319386, WO2010 / 53186, etc.).

[0140] The polyamide imide resin is not limited to the following, for example: the trade name of Toyobo: Vylomax HR11NN, HR16NN, the trade name of RESONAC: HPC-5020, HPC-6000, HPC-7200, HPC-9000, etc.

[0141] As a styrene-based elastomer resin, it is not limited to the following, but may include, for example, block copolymers containing at least one end block of styrene or its analogues and at least one intermediate block of an elastomer block of a conjugated diene or its hydrogenated form. Specific examples include: styrene-butadiene diblock copolymers, styrene-butadiene triblock copolymers, styrene-isoprene diblock copolymers, styrene-isoprene triblock copolymers, hydrogenated styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene triblock copolymers, hydrogenated styrene-isoprene diblock copolymers, hydrogenated styrene-isoprene triblock copolymers, hydrogenated styrene-butadiene random copolymers, etc. As a styrene-based elastomer resin, it is not limited to the following, but may include, for example, Asahi Kasei Corporation's trade names: Asaprene, Tufprene, Asaflex, and Kuraray Corporation's trade names: Hybrar, Septon.

[0142] The polyether resin is not limited to the following, for example, the product manufactured by Sumitomo Chemical Co., Ltd. under the trade name: PES5003P, etc.

[0143] The polyphenylene ether resin is not limited to the following, for example, the Zylon series manufactured by Asahi Kasei Corporation.

[0144] The polysulfone resin is not limited to the following, for example, products manufactured by Solvay Advanced Polymers under the trade names Polysulfone P1700, P3500, etc.

[0145] As an acrylic resin, it is not limited to the following, for example: trade names manufactured by Nagase ChemteX: SG-P3, SG-600LB, SG-280, SG-790, SG-K2, and trade names manufactured by Negami Kogyo Co., Ltd.: SN-50, AS-3000E, ME-2000, etc.

[0146] <Filler> The resin composition of this embodiment may further contain filler. The filler is not limited to the following; from the viewpoint of reducing warpage, examples include: inorganic fillers (inorganic fillers), inorganic fillers pretreated with the following silane coupling agent, and from the viewpoint of improving adhesion strength and crack resistance, examples include: one or more selected from the group consisting of organic fillers. They can be used alone or in combination. Furthermore, the shape of the filler is not particularly limited; for example, it can be any shape, such as irregular, spherical, or scaly. From the viewpoint of making the coefficient of linear expansion of the resin composition of this embodiment close to that of the bonded substrate and reducing warpage, it is preferable to contain inorganic filler.

[0147] The inorganic filler is not limited to the following, but may include, for example: silicon dioxide, alumina, glass, cordierite, polysiloxane, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, magnesium aluminum carbonate, gibbsite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and ceramics such as zirconium tungstate phosphate, carbon nanotubes, graphene, and other carbon-based materials, metals or alloys such as gold, silver, copper, nickel, aluminum, zinc, tin, lead, solder, indium, and palladium, and particles coated with a metal film on a polymer core material. Among these, from the viewpoint of further reducing the warpage of the hardened material, silicon dioxide is preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. From the viewpoint of improving the workability of filling materials or resin compositions, a spherical shape is preferred. Commercially available spherical fused silica is not limited to the following, but includes, for example, products manufactured by Admatechs under the trade names SO-C2, SO-C1, SO-E2, and SO-E1.

[0148] Furthermore, when imparting thermal conductivity to the resin composition, the inorganic filler is preferably composed of thermally conductive ceramic particles or metal particles, such as alumina particles, aluminum nitride particles, boron nitride particles, zinc oxide particles, silicon nitride particles, silicon carbide particles, magnesium oxide particles, gold particles, silver particles, nickel particles, and particles coated with such metal films. From the viewpoint of dispersibility, high thermal conductivity, and resistance to oxidation degradation, alumina particles, aluminum nitride particles, boron nitride particles, gold particles, and silver particles are more preferred.

[0149] Furthermore, when imparting magnetism to the resin composition, it is preferable to include magnetic metal oxide powder as an inorganic filler. The magnetic metal oxide powder is not limited to the following, but may include, for example: Fe-Mn ferrite powder, Fe-Mn-Mg ferrite powder, Fe-Mn-Mg-Sr ferrite powder, Fe-Mg-Zn ferrite powder, Fe-Mg-Sr ferrite powder, Fe-Zn-Mn ferrite powder, Fe... Ferrite powders including Cu-Zn, Fe-Ni-Zn, Fe-Ni-Zn-Cu, Fe-Ba-Zn, Fe-Ba-Mg, Fe-Ba-Ni, Fe-Ba-Co, Fe-Ba-Ni-Co, and Fe-Y, as well as iron oxide powders such as iron oxide powder (III) and iron tetroxide powder. Fe-Mn ferrite powders refer to ferrite powders containing both Fe and Mn, while Fe-Mn-Zn ferrite powders refer to ferrite powders containing Fe, Mn, and Zn. Furthermore, examples of magnetic metal powders include: pure iron powder; Fe-Si alloy powder, Fe-Si-Al alloy powder, Fe-Cr alloy powder, Fe-Cr-Si alloy powder, Fe-Ni-Cr alloy powder, Fe-Cr-Al alloy powder, Fe-Ni alloy powder, Fe-Ni-Si alloy powder, Fe-Ni-B alloy powder, Fe-Ni-Mo alloy powder, Fe-Ni-Mo-Cu alloy powder, Fe-Co alloy powder, Fe-Ni-Co alloy powder, Co-based amorphous alloy powder, and other crystalline or amorphous alloy powders. Fe-Cr-Si alloy powder refers to alloy powder containing Fe, Cr, and Si, while Fe-Ni alloy powder refers to alloy powder containing Fe and Ni.

[0150] When inorganic fillers are used as fillers, the content of inorganic fillers in the resin composition of this embodiment can be appropriately set according to the desired performance, and is not limited to the following, preferably 5-98% by mass, more preferably 10-95% by mass, further preferably 15-90% by mass, further preferably 20-88% by mass, even more preferably 25-85% by mass, and particularly preferably 30-80% by mass. By setting it within this range, there is a tendency to exhibit the following effects: the resin component and inorganic filler are within a reasonable range, resulting in excellent adhesion or bonding, dimensional stability, and warpage.

[0151] Organic fillers refer to those that function as stress-relieving impact damping agents. The resin composition of this embodiment, by containing organic fillers, tends to improve adhesion to various connecting components and suppress the generation and progression of filler cracks.

[0152] The organic filler described above is not limited to the following, but may include, for example: acrylic resin, polysiloxane resin, butadiene rubber, polyester, polyurethane, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic rubber, polystyrene, acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), polysiloxane-modified resin, and organic microparticles containing copolymers thereof as components, but is not limited to them. From the viewpoint of improving adhesion, the organic microparticles described above are preferably, for example, (meth)acrylate alkyl ester-butadiene-styrene copolymer, (meth)acrylate alkyl ester-polysiloxane copolymer, polysiloxane-(meth)acrylate copolymer, polysiloxane and (meth)acrylate composites, (meth)acrylate alkyl ester-butadiene-styrene and polysiloxane composites, and (meth)acrylate alkyl ester and polysiloxane composites.

[0153] As the aforementioned organic filler, organic microparticles with a core-shell structure and different compositions of the core and shell layers can also be used. The core-shell type organic microparticles are not limited to the following, but can include, for example, particles with a polysiloxane-acrylic rubber core grafted with acrylic resin, and particles grafted with acrylic resin onto an acrylic copolymer. Due to the low elastic modulus resulting from the presence of core-shell type organic microparticles, there is a tendency to reduce the stress generated at the filler corner and suppress the formation of filler corner cracks. Furthermore, when filler corner cracks occur, the contained core-shell type organic microparticles act as stress relievers, tending to inhibit the progression of filler corner cracks. As the constituent material of the aforementioned core layer, a material with excellent flexibility is preferred. The core layer material is not limited to the following, but may include, for example, polysiloxane elastomers, butadiene elastomers, styrene elastomers, acrylic elastomers, polyolefin elastomers, and polysiloxane / acrylic composite elastomers. On the other hand, the shell layer material is preferably a material with excellent affinity for other components of the semiconductor resin sealant, especially epoxy resin. Examples of shell layer materials include acrylic resin and epoxy resin, but are not particularly limited to these. Among these, acrylic resin is particularly preferred from the viewpoint of affinity for other components of the sealant, especially epoxy resin.

[0154] When using organic fillers as fillers, the content of organic fillers in the resin composition of this embodiment can be appropriately set according to the desired performance, and is not limited to the following: preferably 1 to 20% by mass, more preferably 2 to 18% by mass, and even more preferably 3 to 16% by mass, relative to the total amount of the resin composition. By making the content of organic fillers 1% by mass or more, there is a tendency to produce a stress-relieving effect and obtain an effect of improving adhesion. By making the content of organic fillers 20% by mass or less, there is a tendency to obtain an effect of heat-resistant reflow soldering.

[0155] <Silane Coupling Agent> The resin composition of this embodiment may further contain a silane coupling agent. By containing a silane coupling agent, the affinity between the resin component and the filler or between the resin component and the substrate to be bonded can be improved, and there is a tendency to improve the uniform dispersion of the filler component and the adhesion of the resin composition, which is therefore preferable.

[0156] In this embodiment, "containing silane coupling agent" refers to incorporating the silane coupling agent into the composition of the resin composition by any of the following methods (i) to (iii) in the step of obtaining the resin composition of this embodiment. (i) Method: Pre-treating the filler with silane coupling agent and then formulating the treated filler into the resin composition. (ii) Method: Directly adding the silane coupling agent to the resin composition (integral blending method). (iii) Method: Formulating the resin composition by reacting the silane coupling agent with the end or side chain of the resin used, or by using a resin copolymerized with a monomer and a silane coupling agent as a silanized resin.

[0157] The methods (i) to (iii) above can be any one of them. If it is (i), it is better from the viewpoint that it is less likely to leave alcohol as a byproduct of silane coupling reaction in the system and that the dispersibility of the filler is better. If it is (ii) or (iii), it is better from the viewpoint that it can also act between the resin and the substrate in addition to the resin and the filler, so that the adhesion or bonding is better.

[0158] A silane coupling agent is one in which at least one hydrolyzable group, such as an alkoxy or aryl group, is bonded to a silicon atom. Additionally, alkyl, alkenyl, or aryl groups may be bonded. Furthermore, the alkyl group may be substituted with an amino, alkoxy, epoxy, or (meth)acryloxy group. As a silane coupling agent, from the viewpoint of improving the uniform dispersion of the filler component and improving the adhesion or bonding of the resin composition, it is not limited to the following, but preferably contains one or more silane coupling agents selected from amino silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, styryl silane coupling agents, acrylate silane coupling agents, isocyanate silane coupling agents, sulfide silane coupling agents, vinyl silane coupling agents, silane coupling agents, organosilazane compounds, and titanate coupling agents.

[0159] As a silane coupling agent, it is not limited to the following, but examples include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-2(-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane, etc., aminosilane coupling agents, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Epoxysilane coupling agents such as glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl(dimethoxy)methylsilane, glycidylbutyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; mercaptosilane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptoundecyltrimethoxysilane; styrenesilane coupling agents such as p-styrenetrimethoxysilane; 3-acryloxypropyltrimethoxysilane; 3-methacryloxypropyltrimethoxysilane. Acrylic silane coupling agents such as 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropyldiethoxysilane; isocyanate silane coupling agents such as 3-isocyanopropyltrimethoxysilane; sulfide silane coupling agents such as bis(triethoxysilylpropyl)disulfide and bis(triethoxysilylpropyl)tetrasulfide; methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole silane, and tris(trimethoxypropyl)silane. Silicon-based coupling agents such as tributyltrimethoxysilane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexaphenyldisilazane, trisilane, cyclotrisilane, octamethylcyclotetrasilane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,Organosilazane compounds such as 3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, and tetramethyldisilazane; tetrabutyl titanate dimer; isopropoxyoctanediol titanium; tetrabutyl titanate; octanediol titanium; bis(triethanolamine)diisopropoxytitanium; dihydroxytitanium dilactate; dihydroxybis(ammonium lactate)titanium; bis(dioctylpyrophosphatoxy)titanium ethylene; bis(dioctylpyrophosphatoxy)hydroxyacetic acid titanate; tri-butoxytitanium monostearate; tetrabutyl titanate; tetra(2-ethylhexyl) titanate; tetraisopropylbis(dioctylphosphatoxy)titanium. Tetraoctyl bis(di-tetrazylphosphoxy)titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tetrazylphosphoxy)titanate, trioctyl titanate isopropyl, triisopropylphenylphenyl titanate isopropyl, triisostearyl titanate isopropyl, isostearyldipropylene titanate isopropyl, dimethacrylisostearyl titanate isopropyl, tri(dioctyl phosphate) titanate isopropyl, tri(dodecylbenzenesulfonyl) titanate isopropyl, tri(dioctyl pyrophosphoxy) titanate isopropyl, tri(N-aminoethylaminoethyl) titanate isopropyl, and other titanate coupling agents.

[0160] Among these, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, and organosilazane compounds are preferred. From the viewpoint of filler flowability when used in conjunction with component (A), aminosilane coupling agents are more preferred. As commercially available products, they are not limited to the following, but may include, for example, products manufactured by Shin-Etsu Chemical Co., Ltd. under the trade names: KBM403 (3-glycidoxypropyltrimethoxysilane), KBM803 (3-mercaptopropyltrimethoxysilane), KBE903 (3-aminopropyltriethoxysilane), KBM573 (N-phenyl-3-aminopropyltrimethoxysilane), SZ-31 (hexamethyldisilazane), etc.

[0161] The content of silane coupling agent in the resin composition of this embodiment is not particularly limited. From the viewpoint of improving the dispersibility of the filler, the adhesion or bonding of the resin composition, and suppressing excessive side reactions, it is preferably 0.1 to 2.0 parts by weight relative to 100 parts by weight of filler.

[0162] <Diluent> The diluent is not limited to the following, but may include, for example: dioctyl phthalate, dibutyl phthalate, benzyl alcohol, compounds having (meth)acrylic groups at both ends of a polyepoxide, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, trimethylolpropane type polyfunctional (meth)acrylate, neopentyl terephthalate type polyfunctional (meth)acrylate, dinepentyl terephthalate type polyfunctional (meth)acrylate, etc.

[0163] <Pigment> As a pigment, it is not limited to the following, for example: carbon black, kaolin, chalk, gypsum, antimony trioxide, chlorinated polyether, aerosol, zinc barium white, barite, titanium dioxide, etc.

[0164] <Dye> As a dye, it is not limited to the following, for example: natural dyes such as dyes derived from plants such as madder and indigo, or dyes derived from minerals such as loess and red clay, synthetic dyes such as alizarin and indigo, and fluorescent dyes, etc.

[0165] <Flow modifier> As a flow modifier, it is not limited to the following, for example: organotitanium compounds such as tetraisopropoxide titanium or diisopropoxybis(acetylpyruvate)titanium; organozirconium compounds such as tetra-n-butoxide zirconium or tetraacetylpyruvate zirconium, etc.

[0166] <Tackifier> As a tackifier, it is not limited to the following, for example: animal-based tackifiers such as gelatin; plant-based tackifiers such as polysaccharides or cellulose; chemically synthesized tackifiers such as polyacrylic acid-based, modified polyacrylic acid-based, polyether-based, carbamate-modified polyether-based, and carboxymethyl cellulose-based tackifiers, etc.

[0167] <Reinforcing Agent> The reinforcing agent is not limited to the following, for example: polyvinyl ether powder such as "Sumikaexcel PES" manufactured by Sumitomo Chemical Co., Ltd.; nano-sized functionalized core-shell rubber particles such as "Kane Ace MX" manufactured by Kaneka Co., Ltd.; polysiloxane and other polysiloxane reinforcing agents.

[0168] <Release Agent> As a release agent, it is not limited to the following, for example: fluorinated release agents, polysiloxane release agents, acrylic release agents containing copolymers of glycidyl methacrylate and linear alkyl esters of (meth)acrylate with 16 to 22 carbon atoms.

[0169] <Wetting Agent> The wetting agent is not limited to the following, for example: unsaturated polyester copolymers with acidic groups such as acrylonitrile polyphosphate.

[0170] <Flame retardant> As a flame retardant, it is not limited to the following, for example: bromine-based flame retardants, phosphorus-based flame retardants and inorganic flame retardants, etc.

[0171] <Surfactant> As a surfactant, it is not limited to the following, for example: anionic surfactants such as alkylbenzene sulfonates or alkyl polyoxyethylene sulfates, cationic surfactants such as alkyl dimethyl ammonium salts, amphoteric surfactants such as alkyl dimethyl amine oxides or alkyl carboxylic betaine, and nonionic surfactants such as straight-chain alcohols or fatty acid esters with 25 or more carbon atoms.

[0172] <Stabilizer> As a stabilizer, for example, as a means to improve the storage stability of the resin composition, it is not limited to the following, such as boric acid and cyclic borate compounds, isocyanuric acid, barbituric acid, aluminum chelating agents, etc. Cyclic borate compounds refer to those containing boron in a cyclic structure. From the viewpoint of resin compatibility and curing uniformity, cyclic borate compounds are preferably 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaboranecyclohexane). Furthermore, a single stabilizer may be used, or two or more may be used in combination.

[0173] The amounts of the other components mentioned above can be added in a functionally appropriate amount. For example, pigments and / or dyes are added in an amount that can provide the desired color to the resin composition of this embodiment. Furthermore, manufacturers can appropriately set the amount added according to the formulation or the desired performance.

[0174] [Curved Product] The cured product of this embodiment is a cured product of the resin composition of this embodiment described above. The resin composition of this embodiment can be cured from a low temperature range, and the resulting cured product tends to have excellent strength or heat resistance. As a curing method, for example, the cured product can be obtained by heating the resin composition of this embodiment. As for the heating conditions, if it is a manufacturer, a suitable heating condition can be appropriately set according to the formulation or the desired performance, preferably at 80 to 300°C for 0.1 minutes to 600 minutes, more preferably at 100 to 250°C for 0.1 minutes to 180 minutes, further preferably at 110 to 210°C for 0.1 to 180 minutes, and further preferably at 120 to 180°C for 10 minutes to 150 minutes.

[0175] [Resin Composition and Resin Paste Using the Same] The resin paste of this embodiment contains the resin composition of this embodiment described above. That is, the resin composition of this embodiment and the resin paste using the same can be obtained by mixing the above-mentioned components (A) and (B), a curing resin, and adding other components as needed. As a curing resin, a resin component that is solid at 25°C can be used, and the resin composition of this embodiment can also be obtained as a solid material. In this case, it can be further pulverized into granules or molded into plates as needed, thereby improving operability. Furthermore, as a curing resin, a resin component that is liquid at 25°C can be used, and the resin composition of this embodiment can also be obtained as a paste material. In particular, components (A) and (B) have excellent compatibility with resins and storage stability, thus becoming a uniform paste material, which is better. There are no particular limitations on the mixing method, and methods known to the industry can be used. It is not limited to the following, for example, it can be obtained by thoroughly mixing to uniformity using a melt mixer, a mixing roller such as a three-roll mill, a dispersing mixer, a planetary mixer, a rotary mixer, a kneader, an extruder, etc.

[0176] (Specific form of resin composition and resin paste used therein) The resin composition of this embodiment and the resin paste used therein have excellent storage stability and can be cured at low temperature. Therefore, they can be used as sealing materials for electrical and electronic parts such as underfill adhesives, molding underfill adhesives, relay sealants, and compression molding sealants; various insulating liquid adhesives; insulating materials such as interlayer insulating materials; grain bonding pastes, conductive pastes, thermally conductive pastes, and magnetic pastes; ink materials such as solder resist inks, hole-filling inks, and magnetic inks; matrix materials for fiber-reinforced plastics; impregnation and fixation materials for motor coils; and adhesive materials for bonding metal powder in magnets. The resin composition of this embodiment exhibits sufficient storage stability in applications such as underfill adhesives, molding underfill adhesives, and compression molding sealants. Furthermore, components (A) and (B) show excellent compatibility with the curing resin, resulting in a homogeneous resin composition. Therefore, it ensures uniform sealing during heat filling of minute gaps between semiconductor wafers and substrates or between electronic components. Additionally, it tends to possess good heat resistance and strength, thus providing underfill adhesives, molding underfill adhesives, compression molding sealants, and electronic devices using them that are durable for long-term use and offer excellent long-term connection reliability. Furthermore, for example, in paste materials or ink materials such as grain-adhesive pastes, conductive pastes, thermally conductive pastes, and magnetic pastes, if the resin composition of this embodiment has excellent compatibility between components (A) and (B) and the curing resin, resulting in uniformity, then no particle residue is produced during coating or filling of the paste or ink. This results in a cured material with uniform curing or good adhesion to the substrate, thus exhibiting excellent strength or long-term durability, which is even better. Moreover, by appropriately selecting the above-mentioned fillers according to the application, and formulating one or more of silicon dioxide, conductive fillers, thermally conductive fillers, and magnetic fillers, the effects of the present invention can also be obtained, and the desired grain adhesion, conductivity, thermal conductivity, and magnetism can be imparted.

[0177] [Resin Film] The resin composition of this embodiment can be a resin film. The resin film of this embodiment, for example, has a specified support and a resin layer formed on the support by using the resin composition of this embodiment. The resin film of this embodiment may have a protective layer on the surface of the resin layer opposite to the support, as needed.

[0178] (Support) The support constituting the above-mentioned resin film is preferably a material that can withstand the temperature during solvent drying. Such a support is not limited to the following, but may include, for example: polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. Extended versions of these films may also be used as needed.

[0179] (Protective layer) As a protective layer, it is preferably a material that can sufficiently maintain the smoothness of the surface of the resin layer constituting the above-mentioned resin film. As such a protective layer, it is not limited to the following, and polyethylene film, polypropylene film, polyethylene terephthalate film with easy peel treatment, oriented polypropylene film, etc. can be preferably used.

[0180] (Method for Manufacturing Resin Film) The resin film of this embodiment can be manufactured by sequentially laminating a support, a resin layer, and a protective layer as needed. As a method for laminating the support, resin layer, and protective layer, known methods can be used. The resin composition of this embodiment can be directly cast, or a varnish can be prepared by adding a solvent, then coated and dried to form a resin layer. There are no particular limitations on the casting or coating method; known methods such as a coater, rod coater, die lip coater, die nozzle coater, roller coater, or doctor blade coater can be used. If the coating contains solvent, it can be dried to form a resin layer on the support. There are no particular limitations on the drying method; for example, an oven or hot air blowing can be used. Furthermore, there are no particular limitations on the drying temperature or time. From the viewpoint of thoroughly removing the solvent and suppressing deformation of the support due to overheating and residual reaction of the resin layer during drying, drying is preferably carried out within a temperature range of 50°C to 160°C and a drying time of 1 minute to 30 minutes, more preferably within a temperature range of 80°C to 150°C and a drying time of 3 minutes to 25 minutes. Moreover, the drying temperature can be a fixed temperature or a temperature gradient can be applied. Subsequently, a protective layer is deposited on the formed resin layer as needed, thereby producing a resin film.

[0181] (Specific form of resin film) The resin film of this embodiment is not limited to the following, and can be used as an interlayer insulating film, a film-type solder resist, a sealing sheet for semiconductor packaging, a die-attach film, a conductive film, an anisotropic conductive film (ACF), a non-conductive film (NCF), a thermally conductive film, a magnetic film, etc. In the resin film using the resin composition of this embodiment, the storage stability of the resin layer is excellent, and therefore it has the various stability required in the manufacturing process of the resin film from coating to heating and drying and storage. The obtained hardened layer tends to have excellent adhesion to the substrate, and also has excellent heat resistance or strength, which is better. In addition, components (A) and (B) are uniformly dissolved or dispersed in the resin composition or solvent, so the surface smoothness of the resin film is excellent, and therefore it can also adhere to the substrate without gaps. The above characteristics are common requirements for interlayer insulating films, film-type solder resists, sealing sheets for semiconductor packaging, die-attach films, conductive films, anisotropic conductive films (ACF), non-conductive films (NCF), thermally conductive films, magnetic films, etc. Therefore, the resin film of this embodiment is suitable for such samples.

[0182] [Printed Circuit Board] The printed circuit board of this embodiment has a hardened layer comprising a hardened material containing the resin composition of this embodiment. When manufacturing a printed circuit board using the resin film of this embodiment described above, the resin film manufactured by the above method is bonded to a patterned inner circuit board, and lamination is performed while applying pressure and heating from the support side. The surface of the inner circuit can be roughened beforehand. Lamination is performed under normal pressure or reduced pressure, either in batches or continuously using rollers, but double-sided lamination is preferred. The lamination conditions are preferably a pressing temperature of 70°C to 150°C and a pressing pressure of 0.1 to 1 MPa. Furthermore, to prevent the formation of voids, lamination is preferably performed under reduced pressure of 2 kPa or less. After lamination, the support film is peeled off after cooling to room temperature, and then the resin film deposited on the inner circuit board is heated and hardened to form a hardened layer. The hardening conditions are preferably a hardening temperature of 130 to 200°C and a hardening time of 30 to 120 minutes.

[0183] Next, after laser drilling is performed on the areas that will become vias using carbon dioxide gas lasers, roughening treatment can be performed using oxidants such as manganate, dichromate, or ozone to remove contaminants and improve adhesion to the plating layer. Subsequently, conductive circuits are selectively formed on the hardened layer through electroless plating or electroplating, while conductors are formed on the inner wall of the vias, thereby forming the outer layer circuit. Then, an annealing treatment is performed at 150–200°C for 30–60 minutes to improve the adhesion between the conductive layer and the resin layer. The above manufacturing method is then repeated on the conductive circuit layer obtained in this way using a resin film, thereby forming a multi-layered build-up to manufacture a printed circuit board.

[0184] The cured resin composition of this embodiment tends to have excellent adhesion to the substrate, as well as excellent heat resistance or strength. Therefore, it can be widely used in printed circuit boards such as rigid substrates, flexible substrates, single-area layer substrates, and thin substrates. In particular, it can be better used as an add-layer of multilayer printed circuit boards.

[0185] [Semiconductor Packaging] The semiconductor package of this embodiment has a hardened layer comprising a hardened form of the resin composition of this embodiment. The semiconductor package of this embodiment is obtained by using the resin composition of this embodiment and / or the resin film of this embodiment as a sealant, adhesive, or interlayer insulating material, and then hardening it. Examples of semiconductor packages of this embodiment include the following.

[0186] The semiconductor package of the first example includes the aforementioned circuit board or other circuit substrate and a semiconductor chip mounted on the circuit board. The semiconductor package can be manufactured by bonding the semiconductor chip to the circuit board.

[0187] The bonding conditions between the circuit board and the semiconductor wafer can be any condition in which the terminal electrodes of the semiconductor wafer and the circuit wiring of the substrate are conductively connected. For example, the conditions used in flip-chip mounting of semiconductor wafers can be adopted. Also, for example, the semiconductor wafer and the circuit board can be bonded via an insulating adhesive.

[0188] As a bonding method, an example is a method of bonding by reflowing a semiconductor wafer onto a circuit board. The reflow conditions can be set in the range of 120°C to 300°C. Regarding the gap between the semiconductor wafer and the circuit board, from the viewpoint of ensuring reliability during long-term use, it is preferable to fill it with a resin paste such as an underfill adhesive. Alternatively, a molding underfill adhesive can be used to fill the gap in one step, encapsulating the entire semiconductor wafer. The resin paste described in this embodiment can be used as the underfill adhesive or the molding underfill adhesive.

[0189] Another example of a bonding method is the method of pressing a semiconductor wafer onto a circuit board. As for the pressing conditions, the pressing temperature is typically set to a range of 120°C to 240°C, preferably 130°C to 200°C, and even more preferably 140°C to 180°C. The pressing time is typically in the range of 1 second to 60 seconds, preferably 5 seconds to 30 seconds.

[0190] When bonding is performed by crimping, conductivity can be achieved using NCF or ACF while sealing is performed simultaneously using resin. The aforementioned resin film can be used as the NCF or ACF.

[0191] The second example of the semiconductor package includes a semiconductor wafer and a cured resin composition of this embodiment that seals the semiconductor wafer. In this type of semiconductor package, the cured resin composition of this embodiment typically functions as a sealing layer. Examples of the second example of the semiconductor package include, for instance, Fan-out wafer-level packaging (FO-WLP) or Fan-out panel-level packaging (FO-PLP). In particular, the resin composition of this embodiment has sufficient storage stability, and components (A) and (B) have excellent compatibility with the curable resin, making it suitable as a uniform resin composition. Therefore, it can be better used as a sealing material for WLPs or PLPs that require uniform sealing of large areas. The resulting cured layer tends to have excellent adhesion to the substrate, excellent heat resistance, or excellent strength, and can function better as a sealing layer for WLPs or PLPs. As for the configuration of the Fan-out type WLP, which is one example of semiconductor packaging as a second example, it includes a semiconductor wafer, a sealing layer formed in a manner that covers the periphery of the semiconductor wafer, an insulating layer disposed adjacent to the wafer on the opposite side of the sealing layer, a rewiring layer formed by stacking conductor layers, a solder mask layer, and bumps.

[0192] This semiconductor package manufacturing method includes: (A) a step of depositing a temporary fixing film on a substrate; (B) a step of temporarily fixing a semiconductor wafer onto the temporary fixing film; (C) a step of forming a sealing layer on the semiconductor wafer; (D) a step of peeling the substrate and the temporary fixing film from the semiconductor wafer; (E) a step of forming a rewiring layer on the surface of the substrate and the temporary fixing film after peeling off the semiconductor wafer; and (F) a step of forming a solder resist layer on the rewiring layer. Furthermore, the above semiconductor package manufacturing method may further include: (G) a step of cutting a plurality of semiconductor packages into individual semiconductor packages, thereby achieving monolithic packaging.

[0193] (Step (A)) Step (A) is the step of temporarily fixing the film by laminating it onto the substrate. Examples of substrates include: silicon wafers; glass wafers; glass substrates; metal substrates such as copper, iron, stainless steel, and cold-rolled steel sheets (SPCC); substrates such as FR-4 substrates in which epoxy resin is impregnated into glass fibers and subjected to thermosetting treatment; and substrates containing bismaleimide triterpenoid resins such as BT resin.

[0194] The temporary fixation film can be peeled off from the semiconductor wafer and any material capable of temporarily fixing the semiconductor wafer can be used.

[0195] (Step (B)) Step (B) is the step of temporarily fixing the semiconductor wafer onto the temporary fixing film. The temporary fixing of the semiconductor wafer can be performed using devices such as flip-chip bonders or die bonders. The layout and number of semiconductor wafers can be appropriately set according to the shape and size of the temporary fixing film, the target production quantity of the semiconductor package, etc. For example, the semiconductor wafers can be temporarily fixed by arranging them in a matrix of multiple columns and multiple rows.

[0196] (Step (C)) Step (C) is the step of forming a sealing layer on a semiconductor wafer. The sealing layer can be formed by curing the resin composition of this embodiment. The sealing layer is generally formed by a method including the steps of forming a resin composition layer on a semiconductor wafer and thermally curing the resin composition layer to form a cured layer as a sealing layer. The formation of the resin composition layer on the semiconductor wafer can be performed, for example, by compression molding. In compression molding, a substrate and a resin composition are typically placed in a mold, and pressure and heat, as needed, are applied to the resin composition within the mold to form a resin composition layer on the substrate.

[0197] The specific operation of the compression molding method can be carried out, for example, by the following method. An upper mold and a lower mold are prepared as molds for compression molding. A resin composition is then coated onto a specified substrate. The substrate coated with the resin composition is installed onto the lower mold. Subsequently, the upper and lower molds are locked together, and heat and pressure are applied to the resin composition to perform compression molding.

[0198] Furthermore, the specific operation of the compression molding method can be carried out, for example, by the following method: An upper mold and a lower mold are prepared as molds for compression molding. A resin composition is placed in the lower mold. A substrate and, if necessary, a release film are installed in the upper mold. Then, the upper and lower molds are locked together in such a way that the resin composition placed in the lower mold is in contact with the substrate installed in the upper mold, and heat and pressure are applied to perform compression molding. Alternatively, for example, a substrate and, if necessary, a release film can be installed in the lower mold, and after casting the resin composition onto the substrate, the upper and lower molds can be locked together to perform compression molding.

[0199] Molding conditions vary depending on the composition of the resin composition used, and appropriate conditions are adopted to achieve a good seal. Generally, the mold is removed after the hardened layer of the resin composition has been formed. The mold can be removed before or after the resin composition layer has been heat-cured. From the viewpoint of easy demolding, it is preferable to be in a state of heat curing or semi-curing (stage B) without sticking.

[0200] After forming a resin composition layer on a substrate, the resin composition layer is heated (post-cured) to form a hardened layer. The heat curing conditions of the resin composition layer may vary depending on the type of resin composition. The curing temperature is typically 100°C to 240°C, preferably 120°C to 200°C, and even more preferably 130°C to 180°C. The curing time is typically 5 minutes to 120 minutes, preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 90 minutes.

[0201] (Step (D)) Step (D) is the step of peeling the substrate and the temporary fixing film from the semiconductor wafer. Ideally, the peeling method should be appropriate to the material of the temporary fixing film. Examples of peeling methods include heating, foaming, or expanding the temporary fixing film to peel it off. Another example of a peeling method is irradiating the temporary fixing film with ultraviolet light from the substrate to reduce the adhesion of the temporary fixing film and thus peel it off.

[0202] In methods of peeling off a temporary fixation film by heating, foaming, or expanding, the heating conditions are typically 100°C to 250°C for 1 to 90 seconds or 5 to 15 minutes. Furthermore, in methods of peeling off a temporary fixation film by irradiating it with ultraviolet light to reduce its adhesiveness, the amount of ultraviolet light irradiated is typically 10 mJ / cm² to 1000 mJ / cm².

[0203] If the substrate and temporary fixing film are peeled off from the semiconductor wafer as described above, the surface of the sealing layer is exposed. A method for manufacturing a semiconductor wafer package may include grinding the exposed surface of the sealing layer. Grinding improves the smoothness of the sealing layer surface and suppresses deformation during subsequent rewiring layer formation. The grinding method is not particularly limited; for example, a flat grinding disc can be used.

[0204] (Step (E)) Step (E) is the step of forming a rewiring layer by stacking an insulating layer and a conductor layer on the surface of the substrate and temporary fixing film of the stripped semiconductor wafer. Typically, the rewiring layer is formed on the semiconductor wafer and the sealing layer.

[0205] The material used in the insulating layer of the rewiring layer may be any material with insulating properties, such as that formed by a photosensitive resin composition.

[0206] After forming the insulating layer of the rewiring layer, vias are typically formed in the insulating layer of the rewiring layer to enable interlayer bonding between the semiconductor wafer and the rewiring layer. When the insulating layer of the rewiring layer is formed of a photosensitive resin composition, the method for forming the vias typically includes exposing the surface of the insulating layer of the rewiring layer to a mask. Examples of active energy lines include ultraviolet light, visible light, electron beams, and X-rays. Examples of exposure methods include contact exposure, where the mask is in close contact with the insulating layer of the rewiring layer, and non-contact exposure, where the mask is not in close contact with the insulating layer of the rewiring layer and parallel light is used for exposure.

[0207] Through the above exposure, a latent image can be formed on the insulating layer of the rewiring layer. Therefore, a portion of the insulating layer of the rewiring layer can be removed by subsequent development, thereby forming a via that serves as an opening through the insulating layer of the rewiring layer. Development can be performed using either wet development or dry development. Examples of development methods include: immersion, liquid coating, spraying, brushing, and wiping.

[0208] Subsequently, a conductor layer is formed on the insulating layer where the aforementioned vias are formed. By forming the conductor layer at the location where the vias are formed, the newly formed conductor layer is electrically connected to the conductor layer on the substrate surface, thus achieving interlayer bonding. Examples of methods for forming the conductor layer include plating, sputtering, and vapor deposition. Furthermore, the formation of the insulating layer and conductor layer can be repeated to alternately deposit (stack) the insulating layer and conductor layer.

[0209] (Step (F)) Step (F) is the step of forming a solder mask layer on the rewiring layer. The solder mask layer can be made of any insulating material. From the viewpoint of facilitating the manufacture of semiconductor packages, photosensitive resins and thermosetting resins are preferred. Furthermore, the resin composition of the present invention can be used as a thermosetting resin.

[0210] Furthermore, in step (F), bump fabrication may be performed as needed. Bump fabrication may be performed by methods such as solder balls or solder plating.

[0211] (Step (G)) In addition to steps (A) to (F), the semiconductor package manufacturing method may include step (G) of cutting a plurality of semiconductor packages into individual semiconductor packages, thereby achieving monolithic packaging. There are no particular limitations on the method of cutting semiconductor packages into individual semiconductor packages.

[0212] [Electronic Device] The electronic device of this embodiment includes the printed circuit board and / or semiconductor package described in this embodiment. By using the resin composition of this embodiment, the printed circuit board or semiconductor package of this embodiment can achieve uniform sealing, bonding, or insulation, and has a hardened layer with excellent adhesion, heat resistance, and strength. Therefore, even when installed in miniaturized, high-density electronic devices, it can prevent poor connections or cracks, and it is durable against the heat generated by the increased volume of electronic information processed. Therefore, the resulting electronic device has excellent long-term reliability and is thus superior.

[0213] As an electronic device, there is no particular limitation as long as it is a device that functions by incorporating electronic components. Examples include: various electronic devices used in electrical appliances such as computers, smartphones, game consoles, digital cameras and televisions, vehicles such as motorcycles, automobiles, trams, ships and airplanes, and antennas or servers for high-speed communication.

[0214] The electronic device of this embodiment is not particularly limited. For example, it can be manufactured by mounting various semiconductor chips at the part where the circuit board is connected and making it conductive.

[0215] The method for mounting semiconductor wafers in the manufacture of electronic devices is not limited to the following, and examples include: wire bonding mounting method, flip-chip mounting method, mounting method using bumpless uplayer (BBUL), mounting method using anisotropic conductive film, and mounting method using non-conductive film. During mounting, the resin composition of this embodiment and the resin paste and resin film using it can be used to seal and bond the semiconductor wafer. Furthermore, the method for forming the electronic circuit of the electronic device is not limited to the following, and examples include: circuit forming methods using subtractive, semi-additive, and fully additive methods. During circuit formation, the resin composition of this embodiment and the resin paste and resin film using it can be used to form an insulating layer. In particular, in this embodiment, the resin composition containing component (B) at concentrations of less than 10,000 ppm exhibits excellent adhesion to various substrates, such as metals like copper. Therefore, it displays good adhesion or bonding to the metal circuit portions of electronic circuit components, resulting in electronic circuits with excellent reliability. [Example]

[0216] Hereinafter, specific embodiments and comparative examples will be given to describe this embodiment. However, the present invention is not limited to the following embodiments and comparative examples, and appropriate changes may be made without departing from the spirit of the invention. Furthermore, unless otherwise specified, "parts" and "%" are mass measurements.

[0217] [Ingredient (A-1): Preparation of 2-(2-hydroxyphenyl)imidazole] 17.6 g of salicylaldehyde and 17.4 g of 40% glyoxal aqueous solution were dissolved in 400 mL of methanol, and 64.8 g of ammonium acetate was added. The mixture was stirred at room temperature for 2 hours. After the reaction, methanol was removed by distillation, and 120 mL of water and 300 mL of ethyl acetate were added. Saturated sodium bicarbonate solution was added while stirring until no foaming occurred. The organic layer was separated, and 60 mL of 1 N sulfuric acid aqueous solution and 90 mL of water were added and stirred. The aqueous layer was then separated. Sodium hydroxide was added to the aqueous layer for neutralization, and 400 mL of dichloromethane was added and stirred. The organic layer was then separated. Dichloromethane was removed by distillation from the organic layer, and the mixture was subjected to silicone column chromatography to obtain compound (A-1) as white crystals (referred to as ingredient (A-1) in the table below; the same applies below). The obtained crystals were confirmed by LC-MS to be 2-(2-hydroxyphenyl)imidazole with a purity of 100%.

[0218] [Ingredient (A-2): Preparation of 2-(2-hydroxynaphthyl-1-yl)benzimidazole] 7.6 g of sodium disulfite, 4.33 g of o-phenylenediamine, and 18 mL of dimethylformamide were added to a reactor and stirred at 80°C. 6.89 g of 2-hydroxy-1-naphthaldehyde was dissolved in 18 mL of dimethylformamide and added to the reactor, and the reaction was carried out at 80°C for 4 hours. The reaction solution was added to 100 mL of water. The resulting precipitate was filtered, recovered, and purified by silica gel column chromatography to obtain compound (A-2). The obtained solid was confirmed by LC-MS to be 2-(2-hydroxynaphthyl-1-yl)benzimidazole with a purity of 100%.

[0219] [Preparation of the composition] Component (A) and component (B) were measured in proportions as shown in Tables 1 to 2 below and mixed thoroughly in a mortar to obtain the compositions of Preparation Examples 1 to 17.

[0220] [Preparation of Resin Composition] The above-prepared composition and the curing resin component are measured in proportions as shown in Tables 3 and 4 below, and mixed until fully homogeneous to obtain the resin composition.

[0221] [Methods for Determination and Evaluation of Properties] (Evaluation of Storage Stability: Determination of Thickness Increase Ratio) The viscosity (initial viscosity) of the above-mentioned resin composition was measured at room temperature (25°C) using an E-type viscometer (TVE-35H, manufactured by Toki Sangyo Co., Ltd.). The viscosity after storage at a specified temperature and for a specified time was then measured. The thickness increase ratio was calculated using the following formula (1). The storage temperature was set to 40°C and the storage time was set to 24 hours. Thickness increase ratio (times) = Viscosity after storage / Initial viscosity... Formula (1) As for storage stability, if the thickness increase ratio is 2.0 or less, it is considered good and is marked with ○.

[0222] (Evaluation of Low-Temperature Curing Properties: Evaluation of Curing Time at 110°C) For the resin composition prepared as described above, a dynamic viscosity η'-time curve was obtained using a rheometer (HAAKE MARS, Thermo Scientific) in oscillating mode (f = 1 Hz) when the resin composition was held at 110°C. The time required for the dynamic viscosity η' to reach 10000 Pa·s in the obtained dynamic viscosity η'-time curve was used as the curing time for evaluation. The curing time was evaluated based on the following criteria: <Evaluation Criteria> Less than 17 points: 17 points to 23 points: ○ More than 23 points: ×

[0223] (Evaluation of Adhesion: Copper Plate Shear Adhesion Strength Test) Two copper plates (manufactured by Standard Testpiece, "C1100P", 50 mm in length, 25 mm in width, and 0.5 mm in thickness) were cleaned sequentially with toluene and acetone to degrease them. Two pieces of fluoropolymer tape (manufactured by Chung Hsing Chemical Industry Co., "ASF-110FR", 13 mm in width and 0.08 mm in thickness) were cut to correspond to the 25 mm width of the copper plates and to a length of 25 mm. Using the cut tape as spacers, the tape was attached to the end of each individual copper plate, aligning the width of the copper plate with the length of the tape. Another piece of tape was then attached parallel to the first piece, spaced 5 mm apart. A resin composition prepared as described above was arranged with a 5 mm × 25 mm bonding area surrounded by two pieces of adhesive tape containing spacers. A separate copper plate without spacers was aligned and clamped, covered with adhesive tape, to ensure the bonding surfaces did not shift. After wiping away any excess resin composition, the plate was heated in an oven preheated to 150°C for 1 hour to heat-harden, obtaining a test piece. Five test pieces were prepared in the same manner. The obtained test pieces were subjected to a tensile test using an AUTOGRAPH AGS-X 5kN (manufactured by Shimadzu Corporation) at a speed of 5 mm / min in a constant temperature and humidity chamber at 23°C and 50%RH to determine the tensile shear bond strength. The median value obtained was used as the copper plate shear bond strength. A copper plate shear bond strength of 15 MPa or higher was rated as good and marked with ○. A value less than 15 MPa was marked with ×.

[0224] [Ingredient Description] The following describes the ingredients listed in Tables 1 to 4.

[0225] (Component (A): Compound represented by general formula (1) or (2)) A-1: ​​2-(2-hydroxyphenyl)imidazolium (manufactured in the above [Component (A-1): Manufacturing of 2-(2-hydroxyphenyl)imidazolium]). A-2: 2-(2-hydroxynaphth-1-yl)benzimidazole (manufactured in the above [Component (A-2): Manufacturing of 2-(2-hydroxynaphth-1-yl)benzimidazole]).

[0226] (Component (B): A compound having a structure that acts as a hydrogen bond acceptor) B-1: Imidazole (manufactured by Tokyo Chemical Industry Co., Ltd., pKa of the conjugate acid 7.0) B-2: 1,5-diazabicyclo[4.3.0]-5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd., pKa of the conjugate acid 9.2) B-3: Triphenylphosphine (manufactured by Fujifilm and Koko Pure Chemical Industries Co., Ltd., pKa of the conjugate acid 2.7) B-4: Triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd., pKa of the conjugate acid 10.7) B-5: Pyridine (manufactured by Tokyo Chemical Industry Co., Ltd., pKa of the conjugate acid 5.2) B-6: 2,2'-Biimidazole (manufactured by Tokyo Chemical Industry Co., Ltd., pKa of the conjugate acid 5.0)

[0227] (Curing Resin) EXA850CRP (manufactured by DIC, BisA type epoxy resin, liquid at 25°C, epoxy equivalent 171 g / eq)

[0228] [Preparation Examples 1-17] Each component was prepared by mixing the components according to the mixing ratios (parts by mass) shown in Tables 1-2 below, and by the method described above in [Preparation of Composition]. Furthermore, regarding Preparation Example 17, purified 2-(2-hydroxyphenyl)imidazole itself was used.

[0229] [Examples 1-16], [Comparative Example 1] Using the compositions prepared in Preparation Examples 1-17, each component was mixed at the mixing ratios (parts by mass) shown in Tables 3-4 below, and a resin composition was prepared by the method described above [Preparation of Resin Composition]. The properties of the prepared resin compositions were measured and evaluated by the method described above.

[0230] [Table 1] Ingredients (parts by weight) Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Preparation Example 7 Preparation Example 8 Preparation Example 9 Ingredient(A) A-1 99.99 99.98 99.95 99.9 99.8 99.7 99.45 99.97 99.97 A-2 Component (B) B-1 0.01 0.02 0.05 0.1 0.2 0.3 0.55 B-2 0.03 B-3 0.03 B-4 B-5 B-6 total 100 100 100 100 100 100 100 100 100 Ingredient (B) content / ppm 100 200 500 1000 2000 3000 5500 300 300

[0231] [Table 2] Ingredients (parts by weight) Preparation Example 10 Preparation Example 11 Preparation Example 12 Preparation Example 13 Preparation Example 14 Preparation Example 15 Preparation Example 16 Preparation Example 17 Ingredient(A) A-1 99.5 99.5 99 99.9 99.9 99.9 100 A-2 99.7 Ingredient (B) B-1 1 0.3 B-2 0.5 B-3 0.5 B-4 0.1 B-5 0.1 B-6 0.1 total 100 100 100 100 100 100 100 100 Ingredient (B) content / ppm 5000 5000 10000 3000 1000 1000 1000 0

[0232] [Table 3] Ingredients (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Compositions of imidazole compounds Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Preparation Example 7 Preparation Example 8 Preparation Example 9 3 3 3 3 3 3 3 3 3 Curing resin 100 100 100 100 100 100 100 100 100 Preservation stability ○ ○ ○ ○ ○ ○ ○ ○ ○ Low temperature hardening properties ○ ○ ○ ○ ○ Copper plate bonding strength ○ ○ ○ ○ ○ ○ ○ ○ ○

[0233] [Table 4] Ingredients (parts by weight) Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Comparative Example 1 Compositions of imidazole compounds Preparation Example 10 Preparation Example 11 Preparation Example 12 Preparation Example 13 Preparation Example 14 Preparation Example 15 Preparation Example 16 Preparation Example 17 3 3 3 3 3 3 3 3 Curing resin 100 100 100 100 100 100 100 100 Preservation stability ○ ○ ○ ○ ○ ○ ○ ○ Low temperature hardening properties ○ ○ ○ ○ ○ × Copper plate bonding strength ○ ○ × ○ × × ○ ×

[0234] It is known that in preparation examples 1 to 16 containing component (B), the storage stability is maintained at the same level as in preparation example 17 which does not contain any component (B), and it hardens within 23 minutes at 110°C, and can also harden at low temperatures. Furthermore, from the viewpoint of low-temperature hardening, it is known that compared with the case of preparation examples containing component B-3 which has the structure of general formula (5), the low-temperature hardening performance is higher when using preparation examples containing components B-1 and B-2 which have the structures of general formulas (3) and (4). By using component B-1 which has the structures of general formulas (3) and (4) and is an aromatic heterocyclic amine, the low-temperature hardening performance is even higher. On the other hand, it is known that in preparation example 12 containing 10,000 ppm of component (B) or preparation example 17 which does not contain component (B), the bonding strength of the copper plate decreases. Therefore, it is better for component (B) to be within the range of 10,000 ppm.

[0235] This application is based on Japanese Patent Application No. 2024-140938, filed with the Japan Patent Office on August 22, 2024, and Japanese Patent Application No. 2025-036562, filed with the Japan Patent Office on March 7, 2025, the contents of which are incorporated herein by reference. [Industrial Applicability]

[0236] In addition to sufficient preservation stability, the composition of the present invention has excellent hardening properties at low temperatures and excellent adhesion to substrates such as metals. Therefore, it can be used, for example, as a hardening material, adhesion promoter, rust inhibitor, etc. containing the composition. Furthermore, by containing a curable resin to form a resin composition, or a resin paste or resin film containing such a resin composition, it has industrial applicability in the fields of sealing materials for electrical and electronic components such as underfill adhesives, molding underfill adhesives, relay sealing materials, and compression molding sealing materials; various insulating liquid adhesives; insulating materials such as interlayer insulating materials; grain bonding pastes, conductive pastes, thermally conductive pastes, and magnetic pastes; ink materials such as solder resist inks, hole-filling inks, and magnetic inks; matrix materials for fiber-reinforced plastics; impregnating and fixing materials for motor coils; adhesive materials for bonding metal powder in magnets; or interlayer insulating films, film-type solder resists, sealing sheets for semiconductor packaging, grain bonding films, conductive films, anisotropic conductive films (ACF), non-conductive films (NCF), thermally conductive films, and magnetic films.

Claims

1. A composition comprising component (A): a compound represented by formula (1) below and / or a compound represented by formula (2) below, and component (B): a compound having a structure that serves as an acceptor of hydrogen bonds (except for component (A)); and the content of component (B) is less than 10,000 ppm relative to the total mass of component (A) and component (B); [Chemical 1] (in formula (1), R1 and R2 are each independently selected from the group consisting of hydrogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, and cycloalkyl groups having 6 to 20 carbon atoms that may have substituents, R1 and R2 may be the same or different, and R1 and R2 may be bonded to form a fused ring that does not have aromaticity, X is selected from any one of the group consisting of hydrogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkenyl groups having 2 to 20 carbon atoms that may have substituents, aralkyl groups having 7 to 20 carbon atoms that may have substituents, and heteroarylalkyl groups having 4 to 20 carbon atoms that may have substituents; Y is selected from any one of the group consisting of hydrogen atoms, halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, alkenyl groups having 2 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and acetyl groups having 1 to 20 carbon atoms that may have substituents. When there are multiple Y groups, they may be the same or different. Two or more Y groups may be bonded together to form a monocyclic or fused ring. m is an integer from 1 to 4. [Chemistry 2] In formula (2), X is any one of the following groups: hydrogen atom, alkyl group with 1 to 20 carbon atoms that may have substituents, alkenyl group with 2 to 20 carbon atoms that may have substituents, aralkyl group with 7 to 20 carbon atoms that may have substituents, and heteroarylalkyl group with 4 to 20 carbon atoms that may have substituents. Y and Z are selected from any one of the following groups: hydrogen atom, halogen atom, hydroxyl group, carboxyl group, cyano group, nitro group, alkyl group with 1 to 20 carbon atoms that may have substituents, alkoxy group with 1 to 20 carbon atoms that may have substituents, alkenyl group with 2 to 20 carbon atoms that may have substituents, aryl group with 6 to 20 carbon atoms that may have substituents, aryloxy group with 6 to 20 carbon atoms that may have substituents, and acetyl group with 1 to 20 carbon atoms that may have substituents. Y and Z may be the same or different. Two or more Y groups and two or more Z groups may be bonded to form a monocyclic or fused ring. m and n are independent integers from 1 to 4.

2. The composition of claim 1, wherein the content of the above-mentioned component (B) is 50 ppm or more relative to the total mass of the above-mentioned component (A) and the above-mentioned component (B).

3. The composition of claim 1, wherein the above-mentioned component (B) is a compound having at least one structure selected from the group consisting of formula (3), formula (4), and formula (5) below; [Chemical 3] (in formula (3), the ·· on the nitrogen atom represents a non-shared electron pair) [Chemical 4] (in formula (4), the ·· on the nitrogen atom represents a non-shared electron pair) [Chemical 5] (in formula (5), the ·· on the phosphorus atom represents a non-shared electron pair).

4. The composition of claim 3, wherein the above-mentioned component (B) is a compound containing the structure of the above-mentioned formula (3) and formula (4).

5. The composition of claim 3, wherein the above-mentioned component (B) is an aromatic heterocyclic amine containing the structures of the above-mentioned formula (3) and formula (4).

6. The composition of claim 1, wherein the above-mentioned component (B) contains an imidazole compound.

7. The composition of claim 1, wherein the above-mentioned component (B) contains one or more of the group consisting of imidazole, 4-methylimidazolium, 2-ethyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 4-ethyl-5-methylimidazolium, 4-butyl-5-methylimidazolium, and 2,2'-biimidazole.

8. The composition of claim 1, wherein the molecular weight of the above component (B) is 50,000 or less.

9. The composition of claim 1, wherein in formula (1) above, Y is selected from the group consisting of hydrogen atom, hydroxyl group, carboxyl group, alkoxy group with 1 to 20 carbon atoms without substituents, alkyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, alkoxy group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, aryl group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, aryloxy group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, and acetyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents. In the above formula (2), Y and Z are selected from one of the group consisting of hydrogen atom, hydroxyl group, carboxyl group, alkoxy group with 1 to 20 carbon atoms without substituents, alkyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, alkoxy group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, aryl group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, aryloxy group with 6 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents, and acetyl group with 1 to 20 carbon atoms having hydroxyl and / or carboxyl groups as substituents.

10. The composition of claim 1, wherein in component (A) above, the compound represented by formula (1) is selected from any one of the group consisting of 2-(2-hydroxyphenyl)imidazole, 2-(2-hydroxyphenyl)-4(5)-methylimidazole, 4-ethyl-(2-hydroxyphenyl)-5-methylimidazole, (2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxyphenyl)-5-methylimidazole, and 2-(2-hydroxy-3(5)-methoxyphenyl)imidazole. And / or the compound represented by formula (2) above is selected from any one of the group consisting of 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole, 2-(3-tert-butyl-2-hydroxyphenyl)-5(6)-methylbenzimidazole, 2-(3-tert-butyl-5-tert-butyl-2-hydroxyphenyl)benzimidazole, 2-(3-tert-butyl-5-tert-butyl-2-hydroxyphenyl)-5(6)-methylbenzimidazole, 2-(1-hydroxynaphthyl-2-yl)benzimidazole, 2-(2-hydroxynaphthyl-1-yl)benzimidazole, and 2-(2-hydroxyphenyl)benzimidazole-6-carboxylic acid.

11. A composition comprising component (A): a compound represented by formula (1) below and / or a compound represented by formula (2) below, and component (B): a compound having a structure that serves as an acceptor of hydrogen bonds (except for component (A)); and component (B) contains an imidazole compound; [Chemical 1] (in formula (1), R1 and R2 are each independently selected from the group consisting of hydrogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, halogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, and cycloalkyl groups having 6 to 20 carbon atoms that may have substituents, R1 and R2 may be the same or different, and R1 and R2 may be bonded to form a fused ring that is not aromatic, X is selected from any one of the group consisting of hydrogen atoms, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkenyl groups having 2 to 20 carbon atoms that may have substituents, aralkyl groups having 7 to 20 carbon atoms that may have substituents, and heteroarylalkyl groups having 4 to 20 carbon atoms that may have substituents; Y is selected from any one of the group consisting of hydrogen atoms, halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, alkyl groups having 1 to 20 carbon atoms that may have substituents, alkoxy groups having 1 to 20 carbon atoms that may have substituents, alkenyl groups having 2 to 20 carbon atoms that may have substituents, aryl groups having 6 to 20 carbon atoms that may have substituents, aryloxy groups having 6 to 20 carbon atoms that may have substituents, and acetyl groups having 1 to 20 carbon atoms that may have substituents. When there are multiple Y groups, they may be the same or different. Two or more Y groups may be bonded together to form a monocyclic or fused ring. m is an integer from 1 to 4. [Chemistry 2] In formula (2), X is any one of the following groups: hydrogen atom, alkyl group with 1 to 20 carbon atoms that may have substituents, alkenyl group with 2 to 20 carbon atoms that may have substituents, aralkyl group with 7 to 20 carbon atoms that may have substituents, and heteroarylalkyl group with 4 to 20 carbon atoms that may have substituents. Y and Z are selected from any one of the following groups: hydrogen atom, halogen atom, hydroxyl group, carboxyl group, cyano group, nitro group, alkyl group with 1 to 20 carbon atoms that may have substituents, alkoxy group with 1 to 20 carbon atoms that may have substituents, alkenyl group with 2 to 20 carbon atoms that may have substituents, aryl group with 6 to 20 carbon atoms that may have substituents, aryloxy group with 6 to 20 carbon atoms that may have substituents, and acetyl group with 1 to 20 carbon atoms that may have substituents. Y and Z may be the same or different. Two or more Y groups and two or more Z groups may be bonded to form a monocyclic or fused ring. m and n are independent integers from 1 to 4.

12. A hardener comprising a composition as claimed in any one of claims 1 to 11.

13. An adhesive comprising a composition as claimed in any one of claims 1 to 11.

14. A rust inhibitor comprising a composition as claimed in any one of claims 1 to 11.

15. A resin composition comprising a composition of any one of claims 1 to 11 and a curable resin.

16. The resin composition of claim 15, wherein the curing resin contains an epoxy resin.

17. The resin composition of claim 16, wherein the epoxy resin comprises an epoxy resin that is liquid at 25°C.

18. A cured material, which is a cured material of the resin composition as claimed in claim 15.

19. A resin paste comprising the resin composition of claim 15.

20. A resin film comprising the resin composition of claim 15.

21. A printed circuit board having a hardened layer comprising a hardened material of a resin composition as claimed in claim 15.

22. A semiconductor package having a hardened layer comprising a hardened material of a resin composition as claimed in claim 15.

23. An electronic device having a printed circuit board as claimed in claim 21.

24. An electronic device having a semiconductor package as claimed in claim 22.