Compositions, epoxy resin compositions, films, printed wiring boards, semiconductor wafer packaging, and electronic devices

Abstract

This invention relates to a composition comprising (b): a compound represented by formula (1) below, and (c): Compounds represented by formula (2) below (excluding compounds represented by formula (1)): (In formula (1), A, B, and C are hydrogen atoms, halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, and alkyl groups with 1 to 20 carbon atoms that may have substituents; l, m, and n are integers 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.; D and E are hydrogen atoms, halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, alkyl groups with 1 to 20 carbon atoms that may have substituents, alkoxy groups with 1 to 20 carbon atoms that may have substituents, etc.; two or more Ds and two or more Es may be bonded together to form a monocyclic or fused ring; o and p are integers from 1 to 4).

Description

Technical Field

[0001] The present invention relates to a composition, an epoxy resin composition, a film, a printed wiring board, a semiconductor chip package, and an electronic device. Prior Art

[0002] Previously, epoxy resins have been used in a wide range of applications such as insulating materials, sealing materials, adhesives, conductive materials, or matrix resins for fiber-reinforced plastics, and impregnating and fixing agents for motor coils for electrical and electronic parts including semiconductor elements.

[0003] Among them, as an adhesive for semiconductor elements or a printed wiring board, an epoxy resin composition having excellent adhesiveness and showing high reliability is used. As constituent components of the above epoxy resin composition, epoxy resins, hardeners reactive with the above epoxy resins, fillers as other components, etc. are usually used.

[0004] In recent years, with the high performance of electronic devices, in electronic circuit board materials such as printed wiring boards, build-up and multi-layerization have been used, and the miniaturization and high density of wirings have been developed. Therefore, low dielectric loss factorization for reducing transmission loss and further low warpage of the substrate are required. Also, in the packaging of semiconductor wafers using the above epoxy resin composition, in order to achieve higher productivity or cost reduction, wafer-level packaging or panel-level packaging has attracted attention. In such packaging, in order to apply the above epoxy resin composition to a large substrate and harden it, low warpage is also required.

[0005] Previously, as an insulating resin material applied to wafer-level packaging or printed wiring boards, for example, there is disclosed an insulating resin material containing a thermosetting resin, an inorganic filler, and a polymer resin having a glass transition temperature of 30°C or lower and having at least one skeleton selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton, and a silicone skeleton, and further having at least one skeleton selected from an amide skeleton, an imide skeleton, and a urethane skeleton (for example, refer to Patent Document 1). [Prior Art Documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2021-95580 Summary of the Invention

[0007] [Problems to be Solved by the Invention] On the other hand, with the multi-layerization accompanying the build-up of electronic circuit board materials, or the popularization of wafer-level packaging or panel-level packaging of semiconductor wafers, an epoxy resin composition capable of further suppressing the warpage of the substrate is required. In addition, the cured product of the epoxy resin composition is required to have excellent mechanical strength and high adhesion strength to fine and high-density wirings. However, there are the following problems: Regarding the various requirements for the epoxy resin composition as described above, the epoxy resin composition disclosed in Patent Document 1 still has room for improvement.

[0008] Therefore, in the present invention, in view of the problems of the above prior art, an object is to provide a composition that can obtain an epoxy resin composition having less warpage of a substrate (including various substrates, sometimes only referred to as a substrate hereinafter) of a cured product of the epoxy resin composition, excellent strength of the cured product, and excellent adhesion strength to a metal adherend. [Technical Means for Solving the Problem]

[0009] The present inventors conducted intensive research and as a result, found that by using a composition containing a compound having a specific structure, an epoxy resin composition having less warpage of a substrate of a cured product, excellent strength of the cured product, and excellent adhesion strength to a metal adherend can be obtained, thereby completing the present invention. That is, the present invention is as follows.

[0010] [1] A composition containing (b): a compound represented by the following formula (1), and (c): a compound represented by the following formula (2) (excluding the compound represented by formula (1)).

[0011] [Chemical Formula 1]

[0012] In formula (1), A, B, and C are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and an acyl group having 1 to 20 carbon atoms which may have a substituent. A, B, and C may be the same or different from each other, and two or more A, two or more B, and two or more C may be bonded to each other to form a monocyclic or condensed ring. l, m, and n are each an integer of 1 to 4.

[0013] [Chemical formula 2]

[0014] In formula (2), X is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and a heteroarylalkyl group having 4 to 20 carbon atoms which may have a substituent. D and E are any one selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and an acyl group having 1 to 20 carbon atoms which may have a substituent. D and E may be the same or different from each other, and two or more Ds and two or more Es may be bonded respectively to form a monocyclic or fused ring. o and p are each an integer from 1 to 4.

[0015] [2] The composition as described in [1] above is a hardening agent. [3] In the composition as described in [1] or [2] above, (b): the mass ratio of the compound represented by formula (1) and (c): the compound represented by the following formula (2) (excluding the compound represented by formula (1)) is (b):(c) = 0.001:100 to 20:80. [4] The composition as described in any one of [1] to [3] above is an adhesion promoter. [5] In the composition as described in any one of [1] to [4] above, in the above (b): the compound represented by formula (1), A, B, and C are each one selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 20 carbon atoms without a substituent, an alkyl group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an aryl group having 6 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an aryloxy group having 6 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, and an acyl group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent. [6] In the composition as described in any one of [1] to [5] above, in the above (c): the compound represented by formula (2), X is a hydrogen atom, and D and E are each independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 20 carbon atoms without substituents, an alkyl group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an aryl group having 6 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an aryloxy group having 6 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, and an acyl group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent. [7] The composition according to any one of [1] to [6] above, which contains at least any one selected from the group consisting of 2-[[2-(2-hydroxyphenyl)-1H-benzimidazol-1-yl]methyl]phenol, 2-[[2-(2-hydroxy-3-methoxyphenyl)-1H-benzimidazol-1-yl]methyl]-6-methoxyphenol, 2-[[2-(2-hydroxy-1-naphthyl)-1H-benzimidazol-1-yl]methyl]-1-naphthol, and 3-[[2-(2,3-dihydroxyphenyl)-1H-benzimidazol-1-yl]methyl]-1,2-benzenediol as the compound represented by the above (b): formula (1). [8] The composition according to any one of [1] to [7] above, which contains at least any one selected from the group consisting of 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole, 2-(1-hydroxynaphthalen-2-yl)benzimidazole, 2-(2-hydroxynaphthalen-1-yl)benzimidazole, and 2-(2-hydroxyphenyl)benzimidazole-6-carboxylic acid as the compound represented by the above (c): formula (2). [9] An epoxy resin composition, which contains the composition according to any one of [1] to [8] above, and (a): an epoxy resin.

[10] An epoxy resin composition, which contains (b): the compound represented by formula (1), and (a): an epoxy resin.

[0016] [Chemical formula 3]

[0017] In formula (1), A, B, and C are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and an acyl group having 1 to 20 carbon atoms which may have a substituent. A, B, and C may be the same or different from each other, and two or more A's, two or more B's, and two or more C's may be bonded to each other to form a monocyclic or fused ring. l, m, and n are each an integer from 1 to 4.

[0018]

[11] An epoxy resin composition comprising the composition as described in [7] above, and (a): an epoxy resin.

[12] The epoxy resin composition according to any one of [9] to

[11] above, further comprising (d): a filler.

[13] The epoxy resin composition according to any one of [9] to

[12] above, further comprising (e): at least one selected from the group consisting of a phenolic compound, an active ester compound, and a cyanate ester compound.

[14] The epoxy resin composition according to any one of [9] to

[13] above, further comprising (f): a polymer (excluding the above components (a) and (e)).

[15] The epoxy resin composition according to any one of [9] to

[14] above, further comprising (g): a silane coupling agent.

[16] The epoxy resin composition according to any one of [9] to

[15] above, comprising at least one selected from the group consisting of 2-[[2-(2-hydroxyphenyl)-1H-benzimidazol-1-yl]methyl]phenol, 2-[[2-(2-hydroxy-3-methoxyphenyl)-1H-benzimidazol-1-yl]methyl]-6-methoxyphenol, 2-[[2-(2-hydroxy-1-naphthyl)-1H-benzimidazol-1-yl]methyl]-1-naphthol, and 3-[[2-(2,3-dihydroxyphenyl)-1H-benzimidazol-1-yl]methyl]-1,2-benzenediol as the above (b): the compound represented by formula (1), and contains at least any one selected from the group consisting of 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole, 2-(1-hydroxynaphthalen-2-yl)benzimidazole, 2-(2-hydroxynaphthalen-1-yl)benzimidazole, and 2-(2-hydroxyphenyl)benzimidazole-6-carboxylic acid as the compound represented by the above (c): formula (2), The mass ratio of the above (b) and the above (c) is (b):(c) = 0.001:100 to 20:80, The above epoxy resin composition further contains (d): a filler, (e): at least one selected from the group consisting of phenolic compounds, active ester compounds, and cyanate ester compounds, (f): a polymer (excluding the above components (a) and (e)), and (g): a silane coupling agent.

[17] A film having a support and a resin layer on the above support containing the epoxy resin composition according to any one of the above [9] to

[16] .

[18] A printed wiring board having a cured product layer of the epoxy resin composition according to any one of the above [9] to

[16] .

[19] A semiconductor wafer package having a cured product layer of the epoxy resin composition according to any one of the above [9] to

[16] .

[20] An electronic device having the printed wiring board according to the above

[18] .

[21] An electronic device having the semiconductor wafer package according to the above

[19] . [Effects of the Invention]

[0019] According to the present invention, a composition can be provided, which can obtain an epoxy resin composition having less warpage of a substrate having a cured product of the epoxy resin composition, and excellent strength of the cured product and adhesion strength to a metal adherend. Embodiments

[0020] Hereinafter, the mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an illustration for explaining the present invention and is not intended to limit the present invention to the following content. The present invention can be implemented with appropriate changes within the scope of its gist.

[0021] [Composition] The composition of this embodiment contains (b): a compound represented by the following formula (1), and (c): a compound represented by the following formula (2) (excluding the compound represented by formula (1)).

[0022] [Chemical formula 4]

[0023] In formula (1), A, B, and C are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and an acyl group having 1 to 20 carbon atoms which may have a substituent. A, B, and C may be the same or different from each other, and two or more A's, two or more B's, and two or more C's may be bonded to each other to form a monocyclic or fused ring. l, m, and n are each an integer from 1 to 4.

[0024] [Chemical formula 5]

[0025] In formula (2), X is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and a heteroarylalkyl group having 4 to 20 carbon atoms which may have a substituent. D and E are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and an acyl group having 1 to 20 carbon atoms which may have a substituent. D and E may be the same or different from each other, and two or more D's and two or more E's may be bonded to each other to form a monocyclic or fused ring. o and p are each an integer from 1 to 4.

[0026] With the above configuration, the composition of the present embodiment can be used as a curing agent for the following epoxy resin composition. In the cured product of the epoxy resin composition obtained by combining the following (a) epoxy resin, there is a tendency for the warpage of the substrate having the above cured product to be reduced (hereinafter, sometimes referred to as low warpage), and an epoxy resin composition with excellent strength of the cured product and excellent adhesion strength to the metal adherend is obtained.

[0027] (Component (b): Compound represented by formula (1)) The composition of the present embodiment contains (b): a compound represented by the following formula (1) (hereinafter, sometimes referred to as component (b)). Component (b) functions as a curing agent in the epoxy resin composition obtained by combining with the following (a) epoxy resin, and can function as a curing accelerator when an additional curing agent is formulated. Component (b) can be used alone or in combination of two or more. By containing component (b), the epoxy resin composition of the present embodiment has a tendency to have excellent strength of the cured product and adhesiveness to the metal adherend. Furthermore, when the above epoxy resin composition is formed into a film, there is a tendency for excellent film storage stability.

[0028] [Chemical formula 6]

[0029] In formula (1), A, B, and C are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and an acyl group having 1 to 20 carbon atoms which may have a substituent. A, B, and C may be the same or different from each other, and two or more A, two or more B, and two or more C may be bonded to each other to form a monocyclic or condensed ring. l, m, and n are each an integer from 1 to 4.

[0030] The alkyl group having 1 to 20 carbon atoms as A, B, and C above may be linear or branched, and the number of carbon atoms of the alkyl group is preferably 1 to 18, more preferably 1 to 15. Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, decyl, undecyl, etc.

[0031] The alkoxy groups having 1 to 20 carbon atoms for A, B, and C above can be linear or branched, preferably having 1 to 18 carbon atoms, more preferably 1 to 15 carbon atoms. Examples of the alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, hexoxy, 2-ethylhexoxy, etc.

[0032] The alkenyl groups having 2 to 20 carbon atoms for A, B, and C above can be linear or branched, preferably having 2 to 18 carbon atoms, more preferably 2 to 15 carbon atoms. Examples of the alkenyl groups having 2 to 20 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 2-hexenyl, etc.

[0033] The aryl groups having 6 to 20 carbon atoms for A, B, and C above preferably have 6 to 18 carbon atoms, more preferably 6 to 15 carbon atoms. Examples of the aryl groups having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, biphenyl, etc.

[0034] The acyl groups having 1 to 20 carbon atoms for A, B, and C above preferably have 1 to 18 carbon atoms, more preferably 1 to 15 carbon atoms. Examples of the acyl groups having 1 to 20 carbon atoms include acetyl, benzoyl, trimethylacetyl, etc.

[0035] Furthermore, examples of the structure formed by bonding two or more A's or two or more B's or two or more C's to form a monocyclic or condensed ring structure include naphthyl, anthryl, etc.

[0036] Furthermore, the above alkyl, alkoxy, alkenyl, aryl, aryloxy, and acyl groups can have substituents. Examples of the substituents include alkyl, halogen, hydroxyl, carboxyl, alkoxy, nitro, ester, phenyl, etc., preferably alkyl, hydroxyl, carboxyl, alkoxy.

[0037] Regarding the mechanism by which component (b) imparts excellent cured product strength to the epoxy resin composition of the present embodiment below, the following can be considered, but it is not intended to be limited to the following. Component (b) has two phenolic hydroxyl groups and an imidazole ring, so the probability of being introduced into the crosslinked structure during the curing of the epoxy resin in (a) below is relatively high, and the molecular weight of the formed molecular chain can be increased. Furthermore, it can also contribute to increasing the crosslinking point density. From the above viewpoints, component (b) can impart excellent cured product strength to the epoxy resin composition of the present embodiment below.

[0038] As for the mechanism by which component (b) imparts excellent adhesiveness to a metal adherend to the epoxy resin composition of the present embodiment described below, the following can be considered, but it is not intended to be limited to the following. Since component (b) has an imidazole ring and a hydroxyl group, the coordination bonding property of these functional groups with the metal surface is excellent, and the molecular chain containing component (b) formed during the curing of epoxy resin (a) can also be coordinately bonded to the metal adherend, thereby excellent adhesiveness can be imparted. Also, as described in the mechanism for imparting film storage stability below, by making the epoxy resin composition of the present embodiment contain both component (b) and component (c), excellent stability is exhibited. Thereby, during the heat curing of the epoxy resin composition, the epoxy resin composition can be sufficiently wetted and diffused to the unevenness of the metal substrate, and sufficient adhesive area and anchoring effect can be ensured, so excellent adhesiveness to the metal adherend can be imparted. Also, when the epoxy resin composition of the present embodiment is used as an adhesive film, the film of the epoxy resin composition is heated and melted and bonded to the metal substrate. At this time, the stability is excellent, so sufficient low viscosity can be achieved, and it can sufficiently follow the unevenness of the metal substrate, so sufficient adhesive surface area and anchoring effect can be ensured, and thus excellent adhesive strength can be imparted.

[0039] As for the mechanism by which component (b) imparts excellent storage stability to the film containing the epoxy resin composition of the present embodiment described below, the following can be considered, but it is not intended to be limited to the following. Component (b) can function as a curing agent, but under the conditions of the film storage temperature, specifically, under the low temperature conditions of freezing and refrigerating the stored film, and further at room temperature of about 25 to 40 °C, the nitrogen atom at the 3-position of the imidazole ring forms a hydrogen bond with the hydroxyl group of the adjacent hydroxyphenyl group, so the nucleophilicity is inhibited and stabilized. Furthermore, a bulky hydroxybenzyl group is also substituted on the nitrogen atom at the 1-position of the imidazole ring, so the reactivity is inhibited. Also, by making the epoxy resin composition of the present embodiment contain both the following component (c) and component (b), component (c) having a similar structure and component (b) are easily accessible in the epoxy resin composition, and exhibit an intermolecular interaction of forming a hydrogen bond between the nitrogen atom on the imidazole ring and the hydroxyphenyl group, thereby the reactivity of both component (b) and component (c) can be inhibited. On the other hand, the intramolecular or intermolecular hydrogen bond that contributes to the above reaction inhibition dissociates under the heat curing conditions, and sufficient reactivity is exhibited.

[0040] Regarding component (b): In the compound represented by the above formula (1), A, B, and C are each preferably selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 20 carbon atoms without a substituent, an alkyl group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an aryl group having 6 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an aryloxy group having 6 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, and an acyl group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent. By making A, B, and C hydrogen atoms, the cured product obtained using the epoxy resin composition of the present embodiment can be further reduced in dielectric loss factor. Furthermore, when A, B, and C are a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 20 carbon atoms without a substituent, an alkyl group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an alkoxy group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an aryl group having 6 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an aryloxy group having 6 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, or an acyl group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, the coordination bonding property to a substrate such as a metal increases. Therefore, in the following epoxy resin composition, there is a tendency to improve the adhesion or bonding strength.

[0041] As the above component (b): The compound represented by the formula (1) preferably contains at least any one selected from the group consisting of 2-[[2-(2-hydroxyphenyl)-1H-benzimidazol-1-yl]methyl]phenol, 2-[[2-(2-hydroxy-3-methoxyphenyl)-1H-benzimidazol-1-yl]methyl]-6-methoxyphenol, 2-[[2-(2-hydroxy-1-naphthyl)-1H-benzimidazol-1-yl]methyl]-1-naphthol, and 3-[[2-(2,3-dihydroxyphenyl)-1H-benzimidazol-1-yl]methyl]-1,2-benzenediol. From the viewpoint of the coordination bonding property to a metal substrate due to less steric hindrance and the intermolecular hydrogen bond formation property between the following component (c) and component (b), it is more preferable to contain 2-[[2-(2-hydroxyphenyl)-1H-benzimidazol-1-yl]methyl]phenol. The structure of 2-[[2-(2-hydroxyphenyl)-1H-benzimidazol-1-yl]methyl]phenol is represented by the following formula (I).

[0042] [Chemical formula 7]

[0043] The content of component (b) in the epoxy resin composition obtained by combining the composition of the present embodiment with the following (a) epoxy resin can be appropriately set according to the desired properties and is not particularly limited. From the viewpoints of exhibiting excellent cured product strength, adhesion to a metal adherend, and further film storage stability during film formation, it is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, still more preferably 0.001% by mass or more, still more preferably 0.01% by mass or more, and further preferably 0.03% by mass or more in all non-volatile components after removing the solvent. Also, from the viewpoint of the storage stability of the film using the epoxy resin composition, the content of component (b) is preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less in all non-volatile components after removing the solvent.

[0044] Regarding the method of adding component (b) in the epoxy resin composition obtained by combining the composition of the present embodiment with the following (a) epoxy resin, component (b) can be added when mixing with other components, or can be generated in the system after mixing other components. Also, it can be generated and added when manufacturing the following component (a): epoxy resin, the following components (c) to (g), and other specified additives. The epoxy resin composition of the present embodiment has the following characteristics: Component (b) is a necessary constituent component distinct from the following component (c). Thereby, an epoxy resin composition excellent in cured product strength and storage stability is obtained.

[0045] (Component (c): the compound represented by formula (2)) The composition of the present embodiment contains the compound represented by the following formula (2) (hereinafter, sometimes referred to as component (c)). (c): The compound represented by formula (2) does not include the compound represented by the above formula (1). That is, component (c) is a compound different from the above component (b). The above component (c) can function as a curing agent in the epoxy resin composition of the present embodiment, and can function as a curing accelerator when another curing agent is further contained. On the other hand, by containing component (c), there is a tendency for the low warpage property of the substrate of the cured product of the following epoxy resin composition to be excellent.

[0046] [Chemical formula 8]

[0047] In the above formula (2), X is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and a heteroarylalkyl group having 4 to 20 carbon atoms which may have a substituent. D and E are each independently any one selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and an acyl group having 1 to 20 carbon atoms which may have a substituent. D and E may be the same or different from each other, and two or more D's and two or more E's may be bonded respectively to form a monocyclic or fused ring. o and p are each an integer from 1 to 4.

[0048] In the above formula (2), the alkenyl group having 2 to 20 carbon atoms as X may be linear or branched, and the number of carbon atoms of the alkenyl group is preferably 2 to 18, more preferably 2 to 15. Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 2-hexenyl, etc.

[0049] The aralkyl group having 7 to 20 carbon atoms as X above may be linear or branched, and the number of carbon atoms of the aralkyl group is preferably 7 to 18, more preferably 7 to 15. Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl, phenethyl, naphthylmethyl, etc.

[0050] The heteroarylalkyl group having 4 to 20 carbon atoms as X above may be linear or branched, and the number of carbon atoms of the heteroarylalkyl group is preferably 4 to 18, more preferably 4 to 15. Examples of the heteroarylalkyl group having 4 to 20 carbon atoms include trimethylenemethyl, trimethyleneethyl, 2-pyridylmethyl, 2-pyridylethyl, 3-pyridylmethyl, 3-pyridylethyl, 4-pyridylmethyl, 4-pyridylethyl, etc.

[0051] Furthermore, the above alkyl group, alkenyl group, aralkyl group or heteroarylalkyl group may have a substituent. Examples of the substituent include a halogen group, a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an amino group, an ester group, an arylsulfonyl group, an alkylsulfonyl group, a phenyl group, etc., and preferably a cyano group, an alkoxy group, an amino group, an ester group, a phenyl group.

[0052] The alkyl group having 1 to 20 carbon atoms in D and E above may be linear or branched, preferably having 1 to 18 carbon atoms, more preferably 1 to 15 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, decyl, undecyl, and the like.

[0053] The alkoxy group having 1 to 20 carbon atoms in D and E above may be linear or branched, preferably having 1 to 18 carbon atoms, more preferably 1 to 15 carbon atoms. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, hexyloxy, 2-ethylhexyloxy, and the like.

[0054] The alkenyl group having 2 to 20 carbon atoms in D and E above may be linear or branched, preferably having 2 to 18 carbon atoms, more preferably 2 to 15 carbon atoms. Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 2-hexenyl, and the like.

[0055] The aryl group having 6 to 20 carbon atoms in D and E above preferably has 6 to 18 carbon atoms, more preferably 6 to 15 carbon atoms. Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, anthryl, biphenyl, and the like.

[0056] The acyl group having 1 to 20 carbon atoms in D and E above preferably has 1 to 18 carbon atoms, more preferably 1 to 15 carbon atoms. Examples of the acyl group having 1 to 20 carbon atoms include acetyl, benzoyl, trimethylacetyl, and the like.

[0057] In addition, examples of the structure formed by bonding two or more Ds or two or more Es to form a monocyclic or condensed ring structure include naphthyl, anthryl, and the like.

[0058] In addition, the above alkyl group, alkoxy group, alkenyl group, aryl group, aryloxy group, and acyl group may have substituents. Examples of the substituents include alkyl group, halogen atom, hydroxyl group, carboxyl group, alkoxy group, nitro group, ester group, phenyl group, etc., preferably alkyl group, hydroxyl group, carboxyl group, alkoxy group.

[0059] Component (c) is not limited to the following, and examples thereof include the following imidazole compounds. Examples include: 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-(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-methoxyphenyl)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-dimethoxy-2-hydroxyphenyl)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-hydroxynaphthalen-2-yl)benzimidazole, 2-(2-hydroxynaphthalen-1-yl)benzimidazole, 2-(2-hydroxyphenyl)benzimidazole-6-carboxylic acid, etc.

[0060] Component (c) can be used alone or in combination of two or more.

[0061] As component (c): The mechanism by which the compound represented by the above formula (2) imparts excellent low warpage properties to the epoxy resin composition of the present embodiment can be considered as follows, but is not limited to the following. It is considered that due to its structural characteristics, component (c) acts as a chain transfer agent, that is, when the epoxy group reacts with imidazole to open the ring, the hydroxyl phenyl group close to the generated anion provides a proton to stabilize it. Therefore, during the polymerization reaction, the generation of high molecular weight substances and local viscosity increase around the reaction point are suppressed, and a chain extension reaction can occur in the whole system. Therefore, it is considered that the viscosity increase during curing occurs slowly and uniformly, thereby easily relaxing the stress generated during curing, and there is a tendency to reduce warpage in the substrate having the cured product of the epoxy resin composition. The above mechanism is the mechanism generated between the epoxy resin (a) and component (c), so it can also be applied to epoxy resin compositions further containing other hardener components such as phenolic hardeners, active ester hardeners, and cyanate ester hardeners.

[0062] In component (c): among the compounds represented by formula (2), preferably X is a hydrogen atom, and D and E are each independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 20 carbon atoms without substituents, an alkyl group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an aryl group having 6 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an aryloxy group having 6 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, and an acyl group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent. By making X a hydrogen atom, excellent reactivity can be achieved. By making D and E hydrogen atoms, there is a tendency to further reduce the dielectric loss factor of the cured product obtained by using the epoxy resin composition of this embodiment. Furthermore, when D and E are each independently selected from the group consisting of a hydroxyl group, a carboxyl group, an alkoxy group having 1 to 20 carbon atoms without substituents, an alkyl group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an alkoxy group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an aryl group having 6 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, an aryloxy group having 6 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, and an acyl group having 1 to 20 carbon atoms having a hydroxyl group and / or a carboxyl group as a substituent, the coordination bonding property to adherends such as metals increases, and thus there is a tendency to improve the adhesion or bonding strength.

[0063] As component (c): the compound represented by the above formula (2) is preferably 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole, 2-(1-hydroxynaphthalen-2-yl)benzimidazole, 2-(2-hydroxynaphthalen-1-yl)benzimidazole, and 2-(2-hydroxyphenyl)benzimidazole-6-carboxylic acid. From the viewpoints of balancing reactivity and stability, exhibiting low warpage, and forming intermolecular interactions with the above component (b), 2-(2-hydroxyphenyl)benzimidazole is more preferable.

[0064] The content of the component (c) in the epoxy resin composition of the present embodiment described below is not particularly limited. From the viewpoint of obtaining sufficient curability, in all non-volatile components after removing the solvent, it is preferably 0.005% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, even more preferably 0.15% by mass or more, and further preferably 0.2% by mass or more. Also, from the viewpoint of appropriately maintaining the curing rate and maintaining the uniformity of the cured layer, the content of the component (c) in all non-volatile components after removing the solvent is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less, even more preferably 3% by mass or less, and further preferably 2% by mass or less.

[0065] The component (c) can be added when mixing with other components, can also be generated in the system after mixing other components, and can also be generated and added when manufacturing the following component (a), the above component (b), the following components (d) to (g), and additives.

[0066] ((Mass ratio of component (b) to component (c))) In the composition of the present embodiment, from the viewpoint of excellent balance between reactivity and storage stability, the mass ratio of the component (b) to the component (c) is preferably (b):(c)=0.001:100 to 20:80, more preferably 0.01:100 to 15:85, still more preferably 0.1:100 to 10:90, and even more preferably 1:100 to 8:92. The component (c) is a compound with relatively high crystallinity and may remain in a crystalline state in the epoxy resin composition of the present embodiment described below. However, by containing the component (b) having a similar structure and capable of interacting with the component (c), even in trace amounts, the situation where the component (c) remains in a crystalline state as described above can be improved, and there is a tendency that the composition of the present embodiment exhibits excellent reactivity, and the epoxy resin composition of the present embodiment described below shows good cured product strength or adhesiveness.

[0067] [Epoxy resin composition] The epoxy resin composition of the present embodiment contains (a): an epoxy resin (hereinafter, sometimes referred to as (a) epoxy resin, component (a)) and the above (b): a compound represented by the formula (1). A preferred form is when the epoxy resin composition of the present embodiment contains the (a) epoxy resin and the composition of the present embodiment described above.

[0068] In the epoxy resin composition of the present embodiment, from the viewpoints of the strength of the cured product and the adhesiveness to the metal adherend, it is more preferable to contain at least any one selected from the group consisting of 2-[[2-(2-hydroxyphenyl)-1H-benzimidazol-1-yl]methyl]phenol, 2-[[2-(2-hydroxy-3-methoxyphenyl)-1H-benzimidazol-1-yl]methyl]-6-methoxyphenol, 2-[[2-(2-hydroxy-1-naphthyl)-1H-benzimidazol-1-yl]methyl]-1-naphthol, and 3-[[2-(2,3-dihydroxyphenyl)-1H-benzimidazol-1-yl]methyl]-1,2-benzenediol as the above-mentioned component (b): the compound represented by formula (1).

[0069] (Component (a): Epoxy resin) The epoxy resin composition of the present embodiment contains (a): an epoxy resin (hereinafter, sometimes referred to as epoxy resin (a), component (a)). The epoxy resin (a) used in the epoxy resin composition of the present embodiment is not limited to the following. For example, examples include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol AD type epoxy resin, bisphenol AF type epoxy resin, tetrabromobisphenol A type epoxy resin, biphenyl type epoxy resin, dimethylxylenol type epoxy resin, tetrabromobiphenyl type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenyl benzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy resin, methyl hydroquinone type epoxy resin, dibutyl hydroquinone type epoxy resin, resorcinol type epoxy resin, methyl resorcinol type epoxy resin, catechol type epoxy resin, N,N-diglycidyl aniline type epoxy resin and other bifunctional epoxy resins. These can be used alone or in combination of two or more.

[0070] Furthermore, examples include: N,N-diglycidyl amino benzene type epoxy resin, o-(N,N-diglycidyl amino)toluene type epoxy resin, triglycidyl isocyanurate type epoxy resin and other trifunctional epoxy resins. These can be used alone or in combination of two or more.

[0071] Furthermore, examples include: naphthalene type tetrafunctional epoxy resin, tetraglycidyl diaminodiphenylmethane type epoxy resin, diaminobenzene type epoxy resin and other tetrafunctional epoxy resins. These can be used alone or in combination of two or more.

[0072] Furthermore, examples include: polyfunctional epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, tetraphenylethane epoxy resin, dicyclopentadiene epoxy resin, naphthol aralkyl epoxy resin, brominated phenol novolac epoxy resin, etc. One or a combination of two or more of them can be used.

[0073] Furthermore, examples include: diepoxy resins such as (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 glycol diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane - type diglycidyl ether, dicyclopentadiene - type diglycidyl ether. One or a combination of two or more of them can be used.

[0074] Examples also include: triglycidyl ethers of trimethylolpropane, triglycidyl ethers of glycerol, etc. These are triglycidyl epoxy resins. One or a combination of two or more of them can be used.

[0075] Furthermore, examples include: alicyclic epoxy resins such as vinylidene dioxide(3,4 - cyclohexene), 2 - (3,4 - epoxycyclohexyl)-5,1 - spiro-(3,4 - epoxycyclohexyl)-m - dioxane. One or a combination of two or more of them can be used.

[0076] Furthermore, examples include: glycidylamine epoxy resins such as tetraglycidyl bis(aminomethyl)cyclohexane.

[0077] Furthermore, examples include: hydantoin - type epoxy resins such as 1,3 - diglycidyl - 5 - methyl - 5 - ethylhydantoin; and epoxy resins with a polysiloxane backbone such as 1,3 - bis(3 - glycidyloxypropyl)-1,1,3,3 - tetramethyldisiloxane. One or a combination of two or more of them can be used.

[0078] Examples include: 2-ethylhexyl glycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, hydrogenated bisphenol A epoxy resin, polysiloxane-modified epoxy resin, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane-type diglycidyl ether, dicyclopentadiene-type diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, divinylidene(3,4-cyclohexene), 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane, glycidylamine-type epoxy resins such as tetraglycidyl bis(aminomethyl)cyclohexane, 1,3-diglycidyl-5-methyl-5-ethylhydantoin-type epoxy resin, 1,3-bis(3-glycidyloxypropyl)-1,1,3,3-tetramethyldisiloxane-type epoxy resin, phenyl glycidyl ether, tolyl glycidyl ether, p-secondary butylphenyl glycidyl ether, styrene oxide, p-tertiary butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide, n-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-glycidyloxypropyl)-1,1,3,3-tetramethyldisiloxane, glycidyl neodecanoate, etc., and aliphatic epoxy resins and alicyclic epoxy resins that can also be used as reactive diluents. These can be used alone or in combination of two or more.

[0079] In the epoxy resin composition of this embodiment, from the viewpoint of the strength of the cured product, as the epoxy resin (a), it is preferably a liquid epoxy resin having a bisphenol A structure, bisphenol F structure, bisphenol AF structure, naphthalene structure, glycidyl ester structure, glycidylamine structure, phenol novolac structure, cyclohexane structure, cyclohexanedimethanol structure, butadiene structure, or an alicyclic liquid epoxy resin having an ester skeleton.

[0080] As the above-mentioned liquid epoxy resin, it is not limited to the following. For example, it can be cited: trade names manufactured by DIC Corporation: EXA850CRP (Bis A type epoxy resin), EXA830CRP (Bis F type epoxy resin), HP4032, HP4032D, HP4032SS (naphthalene type epoxy resin); trade names manufactured by Mitsubishi Chemical Corporation: jER828US, jER828EL, jER825 (bisphenol A type epoxy resin), jER807, jER1750 (bisphenol F type epoxy resin), jER152 (phenol novolac type epoxy resin), jER630, jER630LSD (glycidylamine type epoxy resin); trade names manufactured by Nippon Steel Chemical & Material Co., Ltd.: ZX1059 (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "ZX1658", "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin); trade names manufactured by Nagase chemteX Corporation: EX-721 (glycidyl ester type epoxy resin); trade names manufactured by Daicel Corporation: Celloxide 2021P (alicyclic epoxy resin having an ester skeleton), Epolead PB-3600 (epoxy resin having a butadiene structure); trade names manufactured by Nippon Soda Co., Ltd.: JP-100, JP-200 (epoxy resin having a butadiene structure); trade names manufactured by Asahi Kasei Corporation: AER9000 (epoxy resin containing a special soft skeleton), etc. These can be used alone or in combination of two or more.

[0081] Furthermore, by containing a solid epoxy resin in the epoxy resin (a), the heat resistance or strength of the obtained cured product can be improved, and thus it is preferably so. As such a solid epoxy resin, a solid epoxy resin having a biphenyl structure, a xylenol structure, a naphthalene structure, a cresol novolac structure, a dicyclopentadiene structure, a triphenol structure, a naphthol structure, an extended naphthalene ether structure, an anthracene structure, a bisphenol A structure, a bisphenol AF structure, a tetraphenylethane structure, a bisphenol acetophenone structure, or a fluorene structure is more preferable.

[0082] The solid epoxy resins are not limited to the following. For example, the following can be cited: trade names of products manufactured by DIC Corporation: HP-4700, HP-4710 (naphthalene-type tetrafunctional epoxy resin), N-690, N-695 (cresol novolak-type epoxy resin), HP-7200, HP-7200H, HP-7200HH (dicyclopentadiene-type epoxy resin), HP-6000, HP-6000L, EXA-7311, EXA-7311-G3, EXA-7311-G4, EXA-7311-G4S (naphthyl ether-type epoxy resin); trade names of products manufactured by Nippon Kayaku Co., Ltd.: EPPN-502H (triphenol-type epoxy resin), NC3000, NC3000H, NC3000L, NC3100 (biphenyl-type epoxy resin), NC-7000L (naphthol novolak-type epoxy resin); trade names of products manufactured by NIPPON STEEL & SUMIKIN CHEMICAL Co., Ltd.: ESN475V, ESN485 (naphthol-type epoxy resin); trade names of products manufactured by Mitsubishi Chemical Corporation: YX4000, YX4000H, YX4000HS, YL6121 (biphenyl-type epoxy resin), YX4000HK (xylenol-type epoxy resin), YX8800 (anthracene-type epoxy resin), YX7700 (novolak-type epoxy resin containing xylene structure), YL7760 (bisphenol AF-type epoxy resin), YL7800 (fluorene-type epoxy resin), jER1010 (bisphenol A-type solid epoxy resin), jER1031S (tetraphenylethane-type epoxy resin); trade names of products manufactured by Osaka Gas Chemicals Co., Ltd.: OGSOL PG-100, CG-500 (fluorene-type epoxy resin), etc. These can be used alone or in combination of two or more.

[0083] As the epoxy resin (a), from the viewpoint of being able to impart the above effects well in balance, it is preferable to use a liquid epoxy resin and a solid epoxy resin in combination. When a liquid epoxy resin and a solid epoxy resin are used in combination, the mass ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.1 to 1:6. By making the mass ratio of the liquid epoxy resin and the solid epoxy resin in the above range, for the epoxy resin composition of the present embodiment, the following are obtained: (I) the adhesiveness and close contact when used in the form of a film become better; (II) sufficient flexibility is obtained when used in the form of a film, and the operability is improved; and (III) a cured product having sufficient fracture strength can be obtained, and the reliability of a printed wiring board, a semiconductor chip package, and an electronic device using them can be improved; etc. effects. From the viewpoint of the effects of the above (I) to (III), the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.3 to 1:5, and more preferably in the range of 1:0.6 to 1:4.

[0084] The epoxy equivalent of the epoxy resin (a) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., still more preferably 80 g / eq. to 2000 g / eq., still more preferably 100 g / eq. to 1000 g / eq., and further preferably 120 to 900 g / eq. By making the epoxy equivalent within the above numerical range, the crosslinking density of the cured product of the epoxy resin composition of the present embodiment becomes sufficient, and a cured product having excellent strength is obtained. The epoxy equivalent is the mass of the resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured in accordance with JIS K7236.

[0085] As the epoxy resin (a), from the viewpoint of obtaining an epoxy resin composition having excellent electrical properties and an excellent balance between curability and storage stability, the total chlorine content contained in the above epoxy resin is preferably 2500 ppm or less, more preferably 2000 ppm or less, still more preferably 1500 ppm or less, and still more preferably 900 ppm or less. Also, from the viewpoint of suppressing excessive reduction, the total chlorine content contained in the epoxy resin (a) is preferably 0.01 ppm or more, more preferably 0.02 ppm or more, still more preferably 0.05 ppm or more, still more preferably 0.1 ppm or more, further preferably 0.2 ppm or more, and particularly preferably 0.5 ppm or more.

[0086] Here, the total chlorine content means the total amount of organic chlorine and inorganic chlorine contained in the epoxy resin (a), and is a value based on the mass of the epoxy resin (a). The total chlorine content of the epoxy resin (a) is measured by the following method. The epoxy resin (a) was repeatedly washed and filtered with xylene until no epoxy resin was present in the xylene as the washing liquid. Next, the filtrate was distilled under reduced pressure at 100°C or lower to obtain the epoxy resin. 1 to 10 g of the obtained epoxy resin sample was accurately weighed so that the titration volume became 3 to 7 mL, dissolved in 25 mL of ethylene glycol monobutyl ether, 25 mL of a propylene glycol solution of 1 N KOH was added thereto, and after boiling for 20 minutes, it was calculated by the titration volume using an aqueous silver nitrate solution.

[0087] The content of the epoxy resin (a) in the epoxy resin composition of the present embodiment can be appropriately set according to the desired performance and is not particularly limited. From the viewpoint of curability, it is preferably 5% by mass or more, more preferably 7.5% by mass or more, still more preferably 10% by mass or more, still more preferably 12% by mass or more, and further preferably 14% by mass or more in all the non-volatile components after removing the solvent. Also, from the viewpoint of the workability of the epoxy resin composition of the present embodiment and the film using the epoxy resin composition of the present embodiment, it is preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, still more preferably 55% by mass or less, and further preferably 50% by mass or less in all the non-volatile components after removing the solvent.

[0088] (Component (d): Filler) The epoxy resin composition of the present embodiment may further contain component (d) filler (hereinafter, sometimes referred to as filler (d), component (d)). As the filler (d), it is not limited to the following. From the viewpoint of reducing the warpage of the substrate of the cured product of the epoxy resin composition of the present embodiment, examples include: inorganic fillers (inorganic fillers), inorganic fillers obtained by pretreating inorganic fillers with the following silane coupling agent (g), and from the viewpoint of improving the adhesion strength and improving the crack resistance, examples include: one or more selected from the group consisting of organic fillers. These can be used alone or in combination of two or more. Also, the shape of the filler (d) is not limited to the following. For example, examples include: irregular shapes, spherical shapes, and scaly shapes, and it can be any of these forms. From the viewpoint of making the linear expansion coefficient of the epoxy resin composition of the present embodiment close to that of the adherend and reducing the warpage of the substrate of the cured product of the epoxy resin composition of the present embodiment, it is preferable to contain an inorganic filler as component (d).

[0089] As the inorganic filler, it is not limited to the following. For example, it can be cited: silica, alumina, glass, cordierite, polysiloxides, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, bauxite, 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 zirconium tungstate phosphate, etc. ceramics, carbon nanotubes, graphene, etc. carbon-based materials, gold, silver, copper, nickel, aluminum, zinc, tin, lead, solder, indium, and palladium, etc. metals or alloys, particles with a metal film coated on a polymer core material, etc. Among them, from the viewpoint of further reducing the warpage of the cured product, it is preferably contains silica. As silica, for example, it can be cited: amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. From the viewpoint of making the filling property or the workability of the epoxy resin composition good, its shape is more preferably spherical. As commercially available spherical fused silica, for example, it can be cited: product names manufactured by Admatechs Co., Ltd.: SO-C2, SO-C1, SO-E2, SO-E1, etc.

[0090] The average particle diameter of the filler (d) is not particularly limited. From the viewpoint of forming a cured layer using the epoxy resin composition containing the above component (d) and being able to form fine wiring on the above cured layer, it is preferably 3 μm or less, more preferably 2 μm or less, and further preferably 1 μm or less, 0.7 μm or less, 0.5 μm or less, 0.4 μm or less, or 0.3 μm or less. On the other hand, when forming a resin paste using the epoxy resin composition of the present embodiment, from the viewpoint of setting an appropriate viscosity and making the resin paste have good workability, the average particle diameter of the component (d): filler is preferably 0.01 μm or more, more preferably 0.03 μm or more, and further preferably 0.05 μm or more, 0.07 μm or more, or 0.1 μm or more. The average particle diameter of the filler can be measured by the laser diffraction-scattering method based on the Mie scattering theory. Specifically, it can be measured by the following method: using a laser diffraction particle size distribution measuring device, making the particle size distribution of the filler based on volume, and taking the median diameter as the average particle diameter. As the laser diffraction particle size distribution measuring device, the product name: HELOS, etc. manufactured by Sympatec Co., Ltd. can be used.

[0091] As the filler (d), in the case of using an inorganic filler, the content of the inorganic filler in the epoxy resin composition of the present embodiment can be appropriately set according to the desired performance, and is not particularly limited. Preferably, it is 5 to 98% by mass, more preferably 10 to 95% by mass, still more preferably 15 to 90% by mass, still more preferably 20 to 88% by mass, further preferably 25 to 85% by mass, and particularly preferably 30 to 80% by mass. By setting it within this range, the epoxy resin composition and the film of the present embodiment can further exhibit the following effects (i) to (iii): (i) It can be maintained at an appropriate viscosity and has excellent workability; (ii) The resin component and the inorganic filler are in an appropriate range, and the adhesion, close contact, and dimensional stability are excellent; (iii) When the resin composition is hardened, the warpage, heat resistance, and fracture strength are excellent.

[0092] The so-called organic filler refers to one having a function as an impact relaxation agent with stress relaxation properties. By containing an organic filler, the epoxy resin composition of the present embodiment has a tendency to further improve the adhesion to various connecting members and suppress the generation and progress of fillet cracks.

[0093] The above-mentioned organic filler is not limited to the following. For example, it can be exemplified: acrylic resin, silicone resin, butadiene rubber, polyester, polyurethane, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic rubber, polystyrene, acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), silicone-modified resin, and organic fine particles such as copolymers containing these as components. From the viewpoint of improving adhesion, as the above-mentioned organic fine particles, preferably, (meth)acrylic acid alkyl ester-butadiene-styrene copolymer, (meth)acrylic acid alkyl ester-silicone copolymer, silicone-(meth)acrylic copolymer, composite of silicone and (meth)acrylic acid, composite of (meth)acrylic acid alkyl ester-butadiene-styrene and silicone, and composite of (meth)acrylic acid alkyl ester and silicone.

[0094] As the above-mentioned organic filler, organic fine particles having a core-shell structure and different compositions of the core layer and the shell layer can also be used. The core-shell type organic fine particles are not limited to the following. For example, it can be exemplified: particles having a poly-silicone-acrylic rubber core and grafted acrylic resin, and particles having acrylic resin grafted on an acrylic copolymer. Due to the low elastic modulus caused by the presence of core-shell organic microparticles, there is a tendency to reduce the stress generated at the fillet portion and suppress the generation of fillet cracks. Also, when fillet cracks occur, the contained core-shell organic microparticles act as stress relaxants and there is a tendency to suppress the progression of fillet cracks. As the constituent material of the above-mentioned core layer, it is preferable to use a material with excellent flexibility. The constituent material of the core layer is not limited to the following. For example, silicone-based elastomers, butadiene-based elastomers, styrene-based elastomers, acrylic-based elastomers, polyolefin-based elastomers, and silicone / acrylic composite elastomers, etc. can be cited. On the other hand, as the constituent material of the above-mentioned shell layer, it is preferable to use a material with excellent affinity for other components of the semiconductor resin encapsulant, especially excellent affinity for epoxy resins. The constituent material of the shell layer is not limited to the following. For example, acrylic resins and epoxy resins, etc. can be cited. Among them, acrylic resins are particularly preferred from the viewpoint of affinity for other components of the encapsulant, especially affinity for epoxy resins.

[0095] When using an organic filler as the filler (d), the content of the organic filler in the epoxy resin composition of the present embodiment can be appropriately set according to the desired performance and is not particularly limited. Among all the non-volatile components after removing the solvent, it is preferably 1 to 20% by mass, more preferably 2 to 18% by mass, and even more preferably 3 to 16% by mass. By making the content of the organic filler 1% by mass or more, there is a tendency to produce a stress relaxation effect and obtain the effect of improving adhesion. By making the content of the organic filler 20% by mass or less, there is a tendency to obtain the effect of heat resistance to reflow soldering.

[0096] (Component (e): phenolic compound, active ester compound, cyanate ester compound) The epoxy resin composition of the present embodiment may further contain at least one selected from the group consisting of phenolic compounds, active ester compounds, and cyanate ester compounds (hereinafter, sometimes referred to as component (e)). The above-mentioned component (e) can function as a curing agent in the epoxy resin composition of the present embodiment. These can be used alone or in combination of two or more.

[0097] As phenolic compounds, they are not limited to the following. For example, they may include: phenol novolak-based compounds, phenolic compounds containing a triazine skeleton, phenol aralkyl compounds, cresol aralkyl compounds, naphthol aralkyl compounds, biphenyl-modified phenol compounds, biphenyl-modified phenol aralkyl compounds, dicyclopentadiene-modified phenol compounds, amino triazine-modified phenol compounds, naphthol novolak compounds, naphthol-phenol co-condensed novolak compounds, naphthol-cresol co-condensed novolak compounds, allyl acryloyl phenol compounds, etc. Preferably, they are phenolic compounds containing a triazine skeleton.

[0098] The so-called phenolic compound containing a triazine skeleton refers to a compound that functions as a curing agent for epoxy resins and has both a triazine skeleton and a structure derived from a phenolic compound in one molecule. It is usually produced by the condensation of a phenolic compound with a compound having a triazine ring such as melamine and benzoguanamine and formaldehyde. By containing a phenolic compound containing a triazine skeleton, the epoxy resin composition of this embodiment can suppress the linear expansion coefficient to a lower level due to the triazine skeleton. Therefore, the warpage of the substrate of the cured product of the epoxy resin composition of this embodiment can be reduced. Also, there is a tendency for the heat resistance, strength, and adhesion to the substrate to become good. Regarding the nitrogen content contained in the phenolic compound containing a triazine skeleton, from the viewpoint of further improving the above heat resistance, strength, and adhesion to the substrate, it is preferably 2% by mass or more, more preferably 4% by mass or more, still more preferably 5% by mass or more, even more preferably 6% by mass or more, and further preferably 7% by mass or more. On the other hand, from the viewpoint of maintaining the stability of the epoxy resin composition of this embodiment and the crosslink density of the cured product within an appropriate range, the nitrogen content contained in the phenolic compound containing a triazine skeleton is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 25% by mass or less, and further preferably 20% by mass or less. Also, from the viewpoint of further increasing the crosslink density, the phenolic compound containing a triazine skeleton preferably contains a phenol novolak structure.

[0099] The phenolic compound containing a triazine skeleton containing a phenol novolak structure is not limited to the following. For example, it may include: products manufactured by DIC Corporation under the trade names: LA3018, LA3018-50P, LA7052, LA7054, LA1356, etc.

[0100] The so-called active ester-based compound refers to a compound that functions as a curing agent for epoxy resins and has an active ester in the molecule. The epoxy resin composition of the present embodiment contains an active ester compound. Due to the reaction between the active ester and the epoxy group, hydroxyl groups, which are factors causing high dielectric loss factors, are not generated in the epoxy resin composition. Therefore, there is a tendency to reduce the dielectric loss factor. The active ester compound is not particularly limited. From the viewpoint of ensuring a high crosslinking density, a compound having two or more active ester groups in one molecule is preferred. Further, from the viewpoints of heat resistance and the like of the epoxy resin composition of the present embodiment, 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 is more preferred. Still more preferably, it is an active ester compound obtained by reacting a carboxylic acid compound with one or more selected from a phenol compound, a naphthol compound, and a thiol compound. Furthermore, it is more preferably an aromatic compound having two or more active ester groups in one molecule, which is obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group. Moreover, it is further preferably an aromatic compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group, and having two or more active ester groups in one molecule of the aromatic compound. The active ester compound may be linear or multi-branched. Also, if the compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, the compatibility with (a) the epoxy resin can be improved. If it is a compound having an aromatic ring, there is a tendency to improve heat resistance.

[0101] Here, the carboxylic acid compound used to obtain the above active ester compound is not limited to the following. For example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. can be cited. In particular, from the viewpoint of the heat resistance of the epoxy resin composition of the present embodiment, as the above carboxylic acid compound, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred. The above thiocarboxylic acid compound is not limited to the following. For example, thioacetic acid, thiobenzoic acid, etc. can be cited. Examples of the phenol compound or naphthol compound used to obtain the above active ester compound are not limited to the following. For example, 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-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadienyl diol, phenol novolac, etc. Among them, from the viewpoints of the heat resistance of the epoxy resin composition of the present embodiment and the solubility in the epoxy resin or solvent, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadienyl diol, phenol novolac are preferred; catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadienyl diol, phenol novolac are more preferred; 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diol, phenol novolac are further preferred; dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diol, phenol novolac are still further preferred; dicyclopentadienyl diol, phenol novolac are even more preferred; and dicyclopentadienyl diol is particularly preferred. Examples of the above thiol compound are not limited to the following. For example, benzenedithiol, trimethylenedithiol, etc. can be cited.

[0102] As the active ester compound, the active ester compounds disclosed in JP-A-2004-277460 and JP-A-2013-40270 can be used, and commercially available active ester compounds can also be used. The commercially available active ester compounds are not limited to the following. For example, they include: trade names manufactured by DIC Corporation: EXB9451, EXB9460, EXB9460S, HPC-8000-65T (active ester compound containing a dicyclopentadiene-type diphenol structure), EXB9416-70BK (active ester compound containing a naphthalene structure), EXB9050L-62M (active ester compound containing a phosphorus atom); trade names manufactured by Mitsubishi Chemical Corporation: DC808 (active ester compound containing an acetylated product of phenol novolac), YLH1026 (active ester compound containing a benzoylated product of phenol novolac), etc.

[0103] The above-mentioned cyanate ester compound means a compound that functions as a curing agent for an epoxy resin and has a cyanate group in the molecule. By containing the cyanate ester compound, the epoxy resin composition of the present embodiment can generate an oxazoline ring or an oxazolidinone ring by reacting with an epoxy group, thereby imparting flexibility to the epoxy resin composition. And by the trimerization of the cyanate group to form a triazine skeleton, there is a tendency to reduce the warpage of the substrate of the cured product of the epoxy resin composition of the present embodiment and particularly improve the heat resistance. Also, when reacting with an epoxy group, it is not easy to generate a hydroxyl group, so there is a tendency to suppress the dielectric loss factor to a lower level.

[0104] As the cyanate ester compound, it is not limited to the following. For example, it can be exemplified by: novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate ester resin, and some of their trimerized prepolymers, etc. As the cyanate ester resin, it is not limited to the following. For example, it can be exemplified by: bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylenephenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanatephenyl)propane, 1,1-bis(4-cyanatephenyl)methane, bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl) sulfide, bis(4-cyanatephenyl) ether and other bifunctional cyanate ester resins, multifunctional cyanate ester resins derived from phenol novolak, cresol novolak, phenolic resins containing dicyclopentadiene structure, etc., and some of their trimerized prepolymers of these cyanate ester resins, etc. These can be used alone or in combination of two or more. As the commercially available cyanate ester resin, for example, it can be exemplified by: the product name manufactured by Mitsubishi Gas Chemical Company: CYTESTER (registered trademark) TA (bisphenol A type cyanate ester resin), etc.

[0105] The above phenolic compounds, active ester compounds, and cyanate ester compounds can be used alone, but from the viewpoint of achieving a low dielectric loss factor in the cured product of the epoxy resin composition in this embodiment, and suppressing the warpage of the substrate of the cured product of the epoxy resin composition in this embodiment to be small and ensuring good adhesion or adhesiveness, it is preferably used in combination of two or more, more preferably in combination of a phenolic compound and an active ester compound, or a phenolic compound and a cyanate ester compound, and even more preferably in combination of a phenolic compound containing a trimer skeleton and an active ester compound, or a phenolic compound containing a trimer ring and a cyanate ester compound.

[0106] There is no particular limitation on the mass ratio of the hardener when combining two phenolic compounds, active ester compounds, and cyanate ester compounds. For those skilled in the art, it can be appropriately set according to the desired physical properties. For example, when combining an active ester compound and a phenolic compound, from the perspective of achieving a lower dielectric loss factor in the cured product of the epoxy resin composition of this embodiment and suppressing warpage of the substrate of the cured product of the epoxy resin composition of this embodiment to a smaller extent and achieving good balance of adhesion or adhesiveness, in the mass ratio, the active ester compound is set to 1, preferably 1:0.05 to 1:1.5, more preferably 1:0.05 to 1:1, still more preferably 1:0.07 to 1:0.8, and even more preferably 1:0.1 to 1:0.6. Also, for example, when combining a cyanate ester compound and a phenolic compound, from the same viewpoints as above, in the mass ratio, the cyanate ester hardener is set to 1, preferably 1:0.05 to 1:2.0, more preferably 1:0.1 to 1:1.5, still more preferably 1:0.2 to 1:1.2, and even more preferably 1:0.3 to 1:1.

[0107] The content of component (e): phenolic compound, active ester compound, cyanate ester compound in the epoxy resin composition of this embodiment can be appropriately set according to the desired performance and is not particularly limited. When the number of epoxy groups of the epoxy resin (a) is set to 1, from the viewpoint of setting the crosslinking density of component (a) with the phenolic compound, active ester compound, and cyanate ester compound within an appropriate range and preventing the remaining of unreacted functional groups, the number of reactive groups of component (e) is preferably 0.1 to 3, more preferably 0.15 to 2.5, still more preferably 0.2 to 2, even more preferably 0.3 to 1.8, further more preferably 0.35 to 1.5, and particularly preferably 0.5 to 1.2. The above preferred ranges are also applicable when using two or more of the phenolic compound, active ester compound, and cyanate ester compound in combination. Here, the so-called "number of epoxy groups" is the value obtained by dividing the mass of each epoxy resin present in the epoxy resin composition by the epoxy equivalent and summing up the values thus obtained for all epoxy resins. Also, the so-called "reactive group" refers to a functional group that can react with an epoxy group, and is the value obtained by dividing the mass of each component of the phenolic compound, active ester compound, and cyanate ester compound present in the epoxy resin composition by the reactive group equivalent and summing up all the values thus obtained.

[0108] (Component (f): Polymer) The epoxy resin composition of this embodiment may contain component (f) polymer (hereinafter, sometimes referred to as polymer (f), component (f)). The polymer (f) is a polymer different from the above component (a) and the above component (e). By containing the polymer (f), when the epoxy resin composition of the present embodiment is formed into a film shape by casting or coating and drying with a certain thickness, cracking or breaking can be prevented and the film shape can be maintained.

[0109] The polymer (f) is not limited to the following. For example, it may include: phenoxy resin, polyvinyl acetal resin, acid anhydride group-containing vinyl resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamide-imide resin, styrene-based elastomer resin, polyethersulfone resin, polyphenylene ether resin, polysulfone resin, acrylic resin, and the like. The polymer (f) may be used alone or in combination of two or more.

[0110] From the viewpoint of obtaining a cured layer having sufficient strength, the weight average molecular weight of the polymer (f) is preferably 5000 or more, more preferably 10000 or more, still more preferably 20000 or more, and even more preferably 25000 or more. Also, from the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the polymer (f) is preferably 300000 or less, more preferably 200000 or less, still more preferably 150000 or less, and even more preferably 130000 or less. The weight average molecular weight of the polymer (f) can be measured, for example, by gel permeation chromatography (GPC). Specifically, the weight average molecular weight (polystyrene conversion) of the polymer (f) can be measured using HLC-8320GPC manufactured by Tosoh Corporation as the measuring device, using Shodex KF-804 / KF-803 / KF-802 / KF-802 manufactured by RESONAC Corporation as the column, using tetrahydrofuran as the mobile phase, measuring at a column temperature of 40°C, and calculating using the calibration curve of standard polystyrene.

[0111] From the viewpoint of increasing the crosslink density of the cured product and making the heat resistance or strength of the cured layer sufficient, the polymer (f) preferably has a functional group containing one or more atoms selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom or a carbon-carbon double bond. Examples of such a functional group include one or more selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, an amino group, a thiol group, an enol group, an enamine group, a ureido group, a cyanate group, an isocyanate group, a thiocyanate group, a diimide group, an alkenyl group, an allene group, and a ketene group. As the acid anhydride group, a carboxylic anhydride group is preferred. Preferred examples of the alkenyl group include a vinyl group, an allyl group, and a styryl group. When the polymer (f) contains such a functional group, the functional group equivalent of the polymer (f) is preferably 100,000 or less, more preferably 90,000 or less, 80,000 or less, 70,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, 30,000 or less, 20,000 or less, 10,000 or less, 8,000 or less, 6,000 or less, or 5,000 or less. The lower limit of the above functional group equivalent is not particularly limited and can usually be 50 or more, 100 or more, etc.

[0112] Hereinafter, the preferred polymer (f) will be described in more detail. According to a known order, a thermoplastic resin having the above functional group further added to the thermoplastic resin shown below can also be preferably used as the component (f).

[0113] As the phenoxy resin, it is not limited to the following. For example, a phenoxy resin having one or more skeletons selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenol novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton can be preferably used. The terminal of the phenoxy resin can be any functional group such as a phenolic hydroxyl group or an epoxy group. As specific examples of the phenoxy resin, the following can be cited: trade names manufactured by Mitsubishi Chemical Corporation: 1256, 4250 (phenoxy resin containing a bisphenol A skeleton), YX8100 (phenoxy resin containing a bisphenol S skeleton), YX6954, YX6954BH30 (phenoxy resin containing a bisphenol acetophenone skeleton), YX7553, YX7553BH30 (phenoxy resin containing a bis(m-cresol) fluorene skeleton), YL6794 (phenoxy resin containing a terpene skeleton), YL7213, YL7290 (phenoxy resin containing a trimethylcyclohexane skeleton), YL7500BH30, YL7769BH30, YL7482, trade names manufactured by Nippon Steel Chemical & Material Co., Ltd.: FX280, FX293 (phenoxy resin containing a bisphenol fluorene skeleton), etc.

[0114] As the polyvinyl acetal resin, it is not limited to the following. For example, the following can be cited: trade names of Electrochemical industry Co., Ltd.: Denka Butyral 4000-2, 5000-A, 6000-C, 6000-EP, trade names manufactured by Sekisui Chemical Co., Ltd.: S-LEC BH series, BX series, KS series (e.g., KS-1), BL series, BM series, etc.

[0115] As the acid anhydride group-containing ethylene resin, it is not limited to the following. For example, it can be obtained by copolymerizing a monomer (f1) containing an acid anhydride group with other monomers (f2). As the monomer (f1) containing an acid anhydride group, it is not limited to the following. For example, the following can be cited: maleic anhydride, itaconic anhydride, methylmaleic anhydride, aconitic anhydride. As the other monomer (f2), as long as it can copolymerize with the monomer (f1) containing an acid anhydride group, there is no particular limitation, and ethylenically unsaturated monomers such as (meth)acrylic acid, (meth)acrylate, and styrene can be used. As the acid anhydride group-containing ethylene resin, it is not limited to the following. For example, the following can be cited: trade names manufactured by Cray Valley Company: EF-30, EF-40, EF-60, EF-80.

[0116] As the polyimide resin, it is not limited to the following. For example, the following can be cited: trade names manufactured by Shin Nippon Rika Co., Ltd.: RIKACOAT SN-20, PN-20, trade names manufactured by DIC Corporation: UNIDIC V-8000, etc. As the polyimide resin, for example, the following can also be cited: a linear polyimide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetracarboxylic dianhydride (Japanese Patent Laid-Open No. 2006-37083), a polyimide containing a polysiloxane skeleton (Japanese Patent Laid-Open Nos. 2002-12667, 2000-319386, International Publication No. 2010 / 53186, etc.), and other modified polyimides.

[0117] As the polyamide-imide resin, it is not limited to the following. For example, the following can be cited: the trade names manufactured by Toyobo Co., Ltd.: Vylomax HR11NN, HR16NN, and the trade names manufactured by RESONAC Co., Ltd.: HPC-5020, HPC-6000, HPC-7200, HPC-9000, etc.

[0118] As the styrene-based elastomer resin, it is not limited to the following. For example, the following can be cited: a block copolymer containing a block of styrene or its analog as at least one terminal block and an elastomeric block containing a conjugated diene or its hydride as at least one intermediate block. Specifically, the following can be cited: styrene-butadiene diblock copolymer, styrene-butadiene triblock copolymer, styrene-isoprene diblock copolymer, styrene-isoprene triblock copolymer, hydrogenated styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene triblock copolymer, hydrogenated styrene-isoprene diblock copolymer, hydrogenated styrene-isoprene triblock copolymer, hydrogenated styrene-butadiene random copolymer, etc. As specific examples of the styrene-based elastomer resin, the following can be cited: the trade names manufactured by Asahi Kasei Corporation: Asaprene, Tufprene, Asaflex, and the trade names manufactured by Kuraray Co., Ltd.: Hybrar, Septon.

[0119] As the polyethersulfone resin, it is not limited to the following. For example, the following can be cited: the trade name PES5003P manufactured by Sumitomo Chemical Co., Ltd., etc.

[0120] As the polysulfone resin, it is not limited to the following. For example, the following can be cited: the trade names Polysulfone P1700, P3500, etc. manufactured by Solvay Advanced Polymers LLC.

[0121] As the polybutadiene resin, it is not limited to the following. For example, it can be exemplified by the trade names of products manufactured by Nippon Soda Co., Ltd.: G-1000, G-3000, GI-1000, GI-3000, the trade names of products manufactured by Idemitsu Petrochemical Co., Ltd.: R-45EPI, the trade names of products manufactured by Daicel Corporation: Epofriend AT501, the trade names of products manufactured by Cray Valley Company: Ricon130, Ricon142, Ricon150, Ricon657, Ricon130MA, etc.

[0122] As the acrylic resin, it is not limited to the following. For example, it can be exemplified by the trade names of products manufactured by Nagase chemteX Corporation: SG-P3, SG-600LB, SG-280, SG-790, SG-K2, the trade names of products manufactured by Negami Kogyo Co., Ltd.: SN-50, AS-3000E, ME-2000, etc.

[0123] Among them, from the viewpoints that the heat resistance or strength of the cured layer obtained by using the epoxy resin composition of the present embodiment becomes sufficient, long-term connection reliability is ensured, compatibility with the epoxy resin (a) is appropriately maintained, and curing uniformity is ensured, as the polymer (f), it is preferably to contain one or more selected from the group consisting of phenoxy resin, polyvinyl acetal resin, acid anhydride group-containing vinyl resin, polyimide resin, polyamide-imide resin, styrene-based elastomer resin, and acrylic resin.

[0124] Further, when the epoxy resin composition of the present embodiment is applied to a material such as a flexible printed circuit board that is bent and incorporated into an electronic device, by containing the polymer (f), low elasticization of the cured layer of the epoxy resin composition can be achieved, and bending or peeling can be suppressed. In applications where such low elasticization is required, as the polymer (f), it is not limited to the following. For example, a resin containing one or more structures selected from polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure in the molecule is preferred because the effect of low elasticization is easily obtained. Further, from the viewpoint that the effect of low elasticization can be obtained even when a thermoplastic resin having a glass transition temperature of 25°C or lower or being liquid at 25°C is contained, it can be preferably used.

[0125] The content of the polymer (f) in the epoxy resin composition of the present embodiment can be appropriately set according to the desired properties and is not particularly limited. From the perspective of ensuring the adhesion or flexibility of the epoxy resin composition of the present embodiment, in all the non-volatile components after removing the solvent, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.2% by mass or more, and even more preferably 1.5% by mass or more. Also, from the perspective of maintaining the heat resistance or strength of the epoxy resin composition of the present embodiment well, in all the non-volatile components after removing the solvent, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0126] (Component (g): Silane Coupling Agent) The epoxy resin composition of the present embodiment may further contain component (g) silane coupling agent (hereinafter, sometimes referred to as silane coupling agent (g), component (g)). By containing silane coupling agent (g), the affinity between the resin component and (d) filler or between the resin component and the adherend can be improved, and the tendency to improve the uniform dispersibility of (d) filler and the adhesion of the epoxy resin composition can be achieved, so it is preferred.

[0127] In the present embodiment, the so-called containing silane coupling agent (g) means that in the step of obtaining the epoxy resin composition of the present embodiment, the silane coupling agent is incorporated into the composition of the epoxy resin composition by any one of the following methods (I) to (III). (Method (I): A method of pre-treating the filler (d) with a silane coupling agent and formulating the treated filler into the epoxy resin composition. (Method (II): A method of directly adding a silane coupling agent to the epoxy resin composition (overall blending method) (Method (III): A method of reacting a silane coupling agent with the resin terminal or side chain of the epoxy resin (a) or polymer (f) used, or using a resin obtained by copolymerizing a monomer and a silane coupling agent as a silanized resin for formulation.

[0128] Any of the methods (I) to (III) above may be used. When the method (I) is used, it is preferable from the viewpoints of less likelihood of alcohol, which is a by-product of the silane coupling reaction, remaining in the system and better dispersibility of the filler. When the method (II) or (III) is used, it is preferable from the viewpoint that when added between the resin and the filler, it can act between the resin and the substrate to be bonded, and can improve the adhesiveness and close contact.

[0129] The silane coupling agent (g) has at least one hydrolyzable group such as an alkoxy group or an aryloxy group bonded to a silicon atom. In addition, an alkyl group, an alkenyl group, or an aryl group may be bonded. Further, the alkyl group may be substituted with an amino group, an alkoxy group, an epoxy group, or a (meth)acryloyloxy group. As the silane coupling agent (g), from the viewpoints of improving the uniform dispersibility of the filler (d) and improving the adhesiveness or close contact of the resin composition, for example, it is preferably a silane coupling agent containing one or more selected from an amino-silane-based coupling agent, an epoxy-silane-based coupling agent, a mercapto-silane-based coupling agent, a styryl-silane-based coupling agent, an acrylate-silane-based coupling agent, an isocyanate-silane-based coupling agent, a sulfide-silane-based coupling agent, a vinyl-silane-based coupling agent, a silane-based coupling agent, an organosilazane compound, and a titanate-based coupling agent.

[0130] The silane coupling agent (g) is not limited to the following. For example, examples include amino-silane-based coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane; epoxy-silane-based coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl(dimethoxy)methylsilane, glycidylbutyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; mercapto-silane-based coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptoundecyltrimethoxysilane; styryl-silane-based coupling agents such as p-styryltrimethoxysilane; acrylate-silane-based coupling agents such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropyldiethoxysilane; and isocyanate-silane-based coupling agents such as 3-isocyanatopropyltrimethoxysilane.

[0131] Further, as the silane coupling agent (g), it is not limited to the following. For example, it may include: sulfur-containing silane coupling agents such as bis(triethoxysilylpropyl) disulfide and bis(triethoxysilylpropyl) tetrasulfide; silane coupling agents such as methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazole silane, trisilane, tert-butyltrimethoxysilane; organosilazane compounds such as hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexaphenyldisilazane, trisilazane, cyclotrisilazane, octamethylcyclotetrasilazane, 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, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane; titanate coupling agents such as tetra-n-butyl titanate dimer, isopropoxyoctanediol titanate, tetra-n-butyl titanate, octanediol titanate, bis(triethanolamineato)diisopropoxytitanium, dihydroxytitanium bis(lactate), dihydroxybis(ammonium lactate)titanium, bis(dioctylpyrophosphoryloxy)ethylenediol titanate, bis(dioctylpyrophosphoryloxy)glycolate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra(2-ethylhexyl) titanate, tetra-isopropylbis(dioctylphosphinito)titanate, tetraoctylbis(di-tridecylphosphinito)titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tridecylphosphinito)titanate, trioctanoyl titanate isopropyl, triisopropylphenylphenyl titanate isopropyl, triisostearoyl titanate isopropyl, isostearoyl diacryloyl titanate isopropyl, dimethylacryloyl isostearoyl titanate isopropyl, tris(dioctyl phosphate)titanate isopropyl, tris(dodecylbenzenesulfonyl)titanate isopropyl, tris(dioctylpyrophosphoryloxy)titanate isopropyl, tris(N-acylethyl·aminoethyl)titanate isopropyl, etc. These silane coupling agents can be used alone or in combination of two or more.

[0132] Among them, amino silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, and organosilazane compounds are preferred, and amino silane coupling agents are more preferred. Examples of commercially available products include: KBM403 (3-glycidoxypropyltrimethoxysilane), KBM803 (3-mercaptopropyltrimethoxysilane), KBE903 (3-aminopropyltriethoxysilane), KBM573 (N-phenyl-3-aminopropyltrimethoxysilane), SZ-31 (hexamethyldisilazane), etc., manufactured by Shin-Etsu Chemical Co., Ltd.

[0133] The content of the silane coupling agent (g) in the epoxy resin composition of the present embodiment is not particularly limited. From the viewpoints of improving the dispersibility of the filler (d), the adhesiveness or close adhesiveness of the epoxy resin composition of the present embodiment, and suppressing excessive side reactions, it is preferably 0.1 to 2.0 parts by mass relative to 100 parts by mass of the filler (d).

[0134] (Preferred form of epoxy resin composition) A preferred form of the epoxy resin composition of the present embodiment is: containing the above-mentioned (a) epoxy resin, the above-mentioned (b) the compound represented by the above formula (1), and the above-mentioned (c) the compound represented by the above formula (2), and satisfying the following conditions. That is, it is preferably as follows: containing at least any one selected from the group consisting of 2-[[2-(2-hydroxyphenyl)-1H-benzimidazol-1-yl]methyl]phenol, 2-[[2-(2-hydroxy-3-methoxyphenyl)-1H-benzimidazol-1-yl]methyl]-6-methoxyphenol, 2-[[2-(2-hydroxy-1-naphthyl)-1H-benzimidazol-1-yl]methyl]-1-naphthol, and 3-[[2-(2,3-dihydroxyphenyl)-1H-benzimidazol-1-yl]methyl]-1,2-benzenediol as the above-mentioned (b): the compound represented by formula (1), and containing at least any one selected from the group consisting of 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole, 2-(1-hydroxynaphthalen-2-yl)benzimidazole, 2-(2-hydroxynaphthalen-1-yl)benzimidazole, and 2-(2-hydroxyphenyl)benzimidazole-6-carboxylic acid as the above-mentioned (c): the compound represented by formula (2), The mass ratio of the above-mentioned (b) to the above-mentioned (c) is (b):(c) = 0.001:100 to 20:80. The above epoxy resin composition further contains (d): filler, (e): at least one selected from the group consisting of phenolic compounds, active ester compounds, and cyanate ester compounds, (f): polymer (excluding the above components (a) and (e)), and (g): silane coupling agent. By having the above configuration, an epoxy resin composition can be obtained that has less warpage of the substrate of the cured product, and excellent strength of the cured product and adhesive strength to the metal adherend.

[0135] (Additive) In the epoxy resin composition of the present embodiment, as needed, in addition to the above components (a) to (g), a compound reactive with the epoxy resin, a diluent, a reactive diluent, a pigment, a dye, a flow regulator, a tackifier, a strengthening agent, a release agent, a wetting agent, a flame retardant, a surfactant, a stabilizer, an adhesion aid, a solvent, etc. may be further contained as additives.

[0136] As the compound reactive with the above (a) epoxy resin, for example, an acid anhydride-based compound, a thiol-based compound, an aromatic amine-based compound, a guanidine-based compound, an imidazole-based compound other than the above formulas (1) and (2), etc. may be cited.

[0137] As the acid anhydride-based compound, it is not limited to the following. For example, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. may be cited. These may be used alone or in combination of two or more.

[0138] As the thiol-based compound, as long as it contains two or more thiol groups in one molecule, it is not limited to the following. For example, 3,3'-dithiobispropionic acid, trimethylolpropane tris(mercaptoacetate), pentaerythritol tetrakis(mercaptoacetate), ethylene glycol dimercaptoacetate, 1,4-bis(3-mercaptobutyryloxy)butane, isocyanuric acid tris[(3-mercaptopropionyloxy)-ethyl] ester, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, etc. From the viewpoint of the impact resistance of the cured product of the epoxy resin composition of the present embodiment, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate) are preferred, and from the viewpoint of low-temperature curability, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate) are more preferred. These may be used alone or in combination of two or more.

[0139] As aromatic amine compounds, they are not limited to the following. For example, aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, diaminodiphenyl sulfone, etc. can be cited.

[0140] As guanidine compounds, they are not limited to the following. For example, dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, toluylguanidine, etc. can be cited. These can be used alone or in combination of two or more.

[0141] As imidazole compounds other than the above formula (1) and formula (2), they are not limited to the following. For example, imidazole, 2-methylimidazole, 4-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, etc. can be cited. These can be used alone or in combination of two or more.

[0142] As diluents, they are not limited to the following. For example, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, etc. can be cited.

[0143] The so-called reactive diluent refers to a compound having a reactive functional group such as an epoxy group or an acryloyl group that can be incorporated into the cured structure, and is a compound that has the effect of reducing the viscosity of the epoxy resin composition by being added to the epoxy resin composition of the present embodiment. As reactive diluents, they are not limited to the following. For example, acrylate compounds or epoxy compounds that can reduce the viscosity without impairing the reactivity can be cited.

[0144] Regarding the acrylate compounds as reactive diluents, they are not limited to the following. For example, compounds having (meth)acryloyl groups at both ends of polyalkylene oxide, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, trimethylolpropane type polyfunctional (meth)acrylate, pentaerythritol type polyfunctional (meth)acrylate, dipentaerythritol type polyfunctional (meth)acrylate, etc. can be cited.

[0145] As for the epoxy compound as a reactive diluent, it is not limited to the following. For example, n-butyl glycidyl ether, tert-butyl glycidyl ether, diglycidylaniline, N,N'-glycidyl-o-toluidine, phenyl glycidyl ether, tolyl glycidyl ether, p-tert-butylphenyl glycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc. can be cited.

[0146] As a reactive diluent, from the viewpoint of being able to form a three-dimensional crosslinking during curing and suppressing the decrease in heat resistance or toughness during curing, a compound containing two or more glycidyl groups in one molecule is preferably used. Furthermore, one kind of reactive diluent can be used alone, or two or more kinds can be used in combination.

[0147] The content of the reactive diluent can be appropriately set according to the desired performance and is not particularly limited. Relative to 100 parts by mass of the epoxy resin (a), it is preferably 1.0 part by mass or more and 30 parts by mass or less. By making the content 1.0 part by mass or more, the increase in viscosity at room temperature of the epoxy resin composition of this embodiment is suppressed. When used as a film for wiring embedding, the tendency of poor embeddability can be suppressed. Also, the decrease in heat resistance or toughness during curing is suppressed, and the generation and progression of fillet cracks are suppressed. On the other hand, by making the content of the reactive diluent 30 parts by mass or less relative to 100 parts by mass of the epoxy resin (a), the decrease in adhesion is suppressed, and the tendency of peeling during the moisture absorption reflow test is suppressed. It is also preferably further contained a reactive diluent for the purpose of suppressing the increase in viscosity generated when highly filling the filler (d).

[0148] As the pigment, it is not limited to the following. For example, kaolin, whiting, gypsum, antimony trioxide, chlorinated polyether, aerosol, lithopone, barite, titanium dioxide, etc. can be cited.

[0149] As the dye, it is not limited to the following. For example, dyes derived from plants such as Rubia argyi and Polygonum tinctorium, or natural dyes such as dyes derived from minerals such as loess and red clay, synthetic dyes such as alizarin and indigo, and in addition, fluorescent dyes, etc. can be cited.

[0150] As the flow regulator, it is not limited to the following. For example, organotitanium compounds such as titanium tetraisopropoxide or diisopropoxybis(acetylacetonate)titanium; organozirconium compounds such as zirconium tetra-n-butoxide or zirconium tetraacetylacetonate, etc. can be cited.

[0151] As a tackifier, it is not limited to the following. For example, it may include: animal tackifiers such as gelatin; vegetable tackifiers such as polysaccharides or cellulose; chemically synthesized tackifiers such as polyacrylic acid-based, modified polyacrylic acid-based, polyether-based, urethane-modified polyether-based, carboxymethyl cellulose, etc.

[0152] As a reinforcing agent, it is not limited to the following. For example, it may include: polyethylenesulfone powder such as "Sumikaexcel PES" manufactured by Sumitomo Chemical Company; nano-sized functional group-modified core-shell rubber particles such as "Kane Ace MX" manufactured by Kaneka Corporation, polysiloxane-based reinforcing agents such as polyorganosiloxane, etc.

[0153] As a release agent, it is not limited to the following. For example, it may include: fluorine-based release agents, polysiloxane-based release agents, acrylic acid-based release agents containing a copolymer of glycidyl (meth)acrylate and a linear alkyl ester having 16 to 22 carbon atoms in (meth)acrylic acid, etc.

[0154] As a wetting agent, it is not limited to the following. For example, it may include: unsaturated polyester copolymer-based wetting agents having an acidic group such as acryloyl polyphosphate, etc.

[0155] As a flame retardant, it is not limited to the following. For example, it may include: bromine-based flame retardants, phosphorus-based flame retardants, and inorganic-based flame retardants, etc. As a bromine-based flame retardant, for example, it may include: tetrabromophenol, etc., but it is not particularly limited thereto. As a phosphorus-based flame retardant, for example, it may include: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and its epoxy derivatives, triphenylphosphine or its derivatives, phosphate esters, condensed phosphate esters, phosphazene compounds, etc., but it is not particularly limited thereto. As a nitrogen-based flame retardant, for example, it may include: melamine polyphosphate, isocyanuric acid, guanidine-based flame retardants, and triazine-based flame retardants, etc., but it is not particularly limited thereto. As an inorganic-based flame retardant compound, for example, it may include: magnesium hydroxide and aluminum hydroxide, etc., but it is not particularly limited thereto. From the viewpoint of heat resistance, a phosphazene compound or magnesium hydroxide is preferred. Also, a phosphazene compound disclosed in Japanese Patent No. 723041 can be used. Furthermore, the flame retardant can be used alone or in combination of two or more. The content of the flame retardant is not particularly limited, and is preferably 5.0 parts by mass or more and 200 parts by mass or less, more preferably 10 parts by mass or more and 100 parts by mass or less, relative to the mass (100 parts by mass) of the epoxy resin (a).

[0156] As the 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 carboxybetaines, nonionic surfactants such as linear alcohols or fatty acid esters having 25 or more carbon atoms, etc. can be cited.

[0157] As the stabilizer, a compound that improves the storage stability of the epoxy resin composition can be used, and it is not limited to the following. For example, boric acid and cyclic borate compounds, isocyanuric acid, barbituric acid, aluminum chelating agents, etc. can be cited. The so-called cyclic borate compound means a compound containing boron in a cyclic structure. From the viewpoints of compatibility with the resin and curing uniformity, the cyclic borate compound is preferably 2,2'-oxybis(5,5'-dimethyl-1,3,2-dioxaborinane). Furthermore, the stabilizer can be used alone or in combination of two or more.

[0158] As the adhesion aid, as long as it is a component added for the purpose of forming a coordination bond with a metal or a substrate material or improving the affinity, it can be widely used. From the viewpoint of further obtaining the effect of forming a good film on the surface of the adherend and thus improving the adhesion, a thiazole-based compound or a triazole-based compound is preferred.

[0159] As the solvent, there is no particular limitation, and known solvents can be used, and it is not limited to the following. For example, hydrocarbons such as benzene, toluene, xylene, cyclohexane, petroleum spirit, solvent naphtha, etc.; ketones such as acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, etc.; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, etc.; alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, butyl cellosolve, butyl carbitol, 2-phenoxyethanol, 1-methoxy-2-propanol, etc.; amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. These can be used alone or in combination of two or more.

[0160] The content of the solvent in the epoxy resin composition of the present embodiment is not particularly limited. When formulating a solvent and using it as a varnish or paste, from the viewpoints of uniformly dissolving various components, controlling the viscosity within an appropriate range, and improving the workability, it is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, still more preferably 15 to 70% by mass, still more preferably 20 to 65% by mass, and further more preferably 25 to 60% by mass, relative to the entire epoxy resin composition. Furthermore, regarding the above content, when the solvent is contained in other components, these solvents are also included, which is the preferred range of the solvent ratio in the entire epoxy resin composition.

[0161] Also, when the epoxy resin composition of the present embodiment is formed into a film, the content of the solvent in the epoxy resin composition layer after drying the solvent is not particularly limited. From the viewpoint of suppressing the generation of bubbles, it is preferably 8% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less, relative to the entire epoxy resin composition. On the other hand, from the viewpoint of good viscosity control during film lamination, it is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and still more preferably 0.01% by mass or more, relative to the entire epoxy resin composition.

[0162] The additive can be added in a functionally equivalent amount. For example, the pigment and / or dye is added in an amount that can provide the desired color to the epoxy resin composition of the present embodiment. Also, for those skilled in the art, the appropriate addition amount can be appropriately set according to the formulation content or the desired performance.

[0163] [Method for manufacturing epoxy resin composition] The epoxy resin composition of the present embodiment can be obtained by containing the above components (a) to (c), optionally adding components (d) to (g) and the above additives and mixing them. The mixing method is not particularly limited either, and methods known to those skilled in the art can be applied. It is not limited to the following. For example, it can be obtained by充分 mixing to uniformity using a mixing roll such as a three-roll mill, a dispersion stirrer, a planetary stirrer, a rotary stirrer, a kneader, an extruder, etc.

[0164] [Specific aspects of epoxy resin composition] As the epoxy resin composition of the present embodiment, the cured product of the epoxy resin composition has less warpage, excellent cured product strength and adhesion strength to a metal adherend, and thus can be used as a sealing material for electrical and electronic parts such as underfill or relay sealant, various insulating liquid adhesives, die attach pastes, conductive pastes, heat conductive pastes and other paste materials, solder resist inks, hole plugging special inks and other ink materials, matrix resins for fiber reinforced plastics, impregnating and fixing materials for motor coils, etc.

[0165] [Film having a resin layer containing an epoxy resin composition] The epoxy resin composition of the present embodiment can be made into a film having a resin layer containing the epoxy resin composition of the present embodiment. The film of the present embodiment, for example, has a specified support and a resin layer formed of the above epoxy resin composition on the support, and may have a protective layer on the surface of the resin layer opposite to the support as needed.

[0166] (Support) As the support constituting the above film, a material that can withstand the temperature during solvent drying is preferred. Such supports are not limited to the following, and 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. can be cited. As these films, those stretched as needed can also be used.

[0167] (Protective layer) As the protective layer, a material that can sufficiently maintain the smoothness of the surface of the resin layer constituting the above film is preferred. Such protective layers are not limited to the following, and polyethylene film, polypropylene film, polyethylene terephthalate film subjected to easy peeling treatment, oriented polypropylene film, etc. can preferably be used.

[0168] (Manufacturing method of film having an epoxy resin composition layer) The film of the present embodiment can be manufactured by sequentially laminating a support, a resin layer, and a protective layer as needed. As the lamination method of the support, resin layer, and protective layer, a known method can be adopted. For example, to prepare the epoxy resin composition of this embodiment containing the above solvent, first, it is coated on a support using a known method such as a coater, rod coater, die lip coater, die nozzle coater, roll coater, knife coater, etc. and dried to form an epoxy resin layer on the support. As the drying method, there is no particular limitation. For example, it can be exemplified by an oven or hot air blowing. Also, there is no particular limitation on the drying temperature or time. From the viewpoint of sufficiently removing the solvent and suppressing the deformation of the support due to overheating and the remaining reaction of the resin layer during drying, it is preferably dried within a temperature range of 50°C to 160°C and a drying time of 1 minute to 30 minutes, more preferably within 80°C to 150°C and 3 minutes to 25 minutes. Furthermore, regarding the drying temperature, it can be a fixed temperature or a temperature gradient can be applied. Subsequently, a protective layer is laminated on the formed resin layer as needed, whereby the film of this embodiment can be manufactured.

[0169] (Specific aspects of the film of this embodiment) The film of this embodiment is not limited to the following. For example, it can be used as an interlayer insulating film, film type solder resist, sealing sheet for semiconductor packaging, die attach film, conductive film, anisotropic conductive film, non-conductive film, heat conductive film, etc. As the epoxy resin composition layer of this embodiment, the warpage of the substrate of the cured product of the epoxy resin composition of this embodiment is reduced, the cured product strength and the adhesion strength to the metal adherend are excellent. Therefore, it is preferable in film applications where warpage is likely to occur in a substrate having a cured product, a higher strength or reliability is required in a thinner cured layer portion, and a firm adhesion to the metal adherend is required. Also, the film using the epoxy resin composition of this embodiment has excellent storage stability, which is also a preferable factor for film applications. The above characteristics are common requirements for an interlayer insulating film, film type solder resist, sealing sheet for semiconductor packaging, die attach film, conductive film, anisotropic conductive film, non-conductive film, heat conductive film, etc. Therefore, the film of this embodiment is suitable for these aspects.

[0170] [Printed wiring board] The printed wiring board of this embodiment has a cured product layer of the epoxy resin composition of this embodiment. When manufacturing a printed wiring board using the film of the present embodiment described above, the film manufactured by the above method is laminated on the patterned inner layer circuit board while applying pressure and heat from the support body side. The surface of the inner layer circuit may be roughened in advance. The lamination is carried out at normal pressure or reduced pressure, either batchwise or continuously using rollers, but double-sided simultaneous lamination is preferred. The lamination conditions at this time are preferably a crimping temperature of 70°C to 150°C and a crimping pressure of 0.1 to 1 MPa. Also, to prevent the generation of voids, it is preferable to carry out lamination under a reduced pressure of 2 kPa or less. After lamination, the support film is peeled off after cooling to room temperature, and then the adhesive film laminated on the inner layer circuit board is heat-cured to form a cured product layer. As the curing conditions, a curing temperature in the range of 130 to 200°C and a curing time of 30 minutes to 120 minutes are preferred.

[0171] Next, the portion to become a via hole is laser drilled with a carbon dioxide gas laser or the like, and then roughened with an oxidizing agent such as permanganate, dichromate, or ozone for the purpose of removing stains and improving the adhesion to the plating layer. Thereafter, a conductor circuit is selectively formed on the cured layer by electroless plating or electroplating, and a conductor is formed on the inner wall of the via hole to form an outer layer circuit. Thereafter, an annealing treatment is carried out at 150 to 200°C for 30 minutes to 60 minutes, whereby the adhesion between the conductor layer and the resin layer can be improved. On the conductor circuit layer thus obtained, the manufacturing method described above is repeated using the film of the present embodiment, whereby a multi-layer build-up can be formed to manufacture a printed wiring board.

[0172] The cured product of the epoxy resin composition of the present embodiment has less warpage, excellent cured product strength and adhesion strength to the metal adherend, and thus can be widely used for printed wiring boards such as rigid substrates, flexible substrates, single-sided laminated substrates, and thin substrates, and is particularly preferably used as a build-up of a multilayer printed wiring board.

[0173] [Semiconductor Chip Package] The semiconductor chip package of the present embodiment has a cured product layer of the epoxy resin composition of the present embodiment. By using the film having a resin layer containing the epoxy resin composition of the present embodiment described above, a semiconductor chip package with a low warpage and excellent strength can be produced. In particular, it is preferably used for wafer-level packaging or panel-level packaging where the low warpage of the substrate is important due to the use of a large-area substrate. The film of the present embodiment can be laminated on both sides or one side of the substrate used. The manufacturing method of the package has been studied variously and can be roughly divided into a fan-in structure and a fan-out structure.

[0174] When manufacturing a semiconductor package with a fan-in structure using the film of the present embodiment manufactured in the above-described manner, for example, the film manufactured by the above method is laminated on a substrate such as a silicon wafer on which a circuit, components, or electrode pads are formed, and is hardened to obtain a hardened layer. The lamination conditions or hardening conditions at this time may be the same as those when manufacturing a printed wiring board, or may be appropriately changed according to the heat resistance of the components used, etc. Subsequently, a redistribution layer is formed by performing an opening process, stain removal, electroless plating, and electroplating on the hardened layer, thereby obtaining a circuit layer. Further, lamination and circuit layer formation are repeated as needed, whereby a multilayer circuit can be formed. Thereafter, solder balls are arranged in a manner to achieve electrical connection with the circuit layer, and dicing is performed to singulate, whereby a package with a fan-in structure of the present invention can be manufactured. Furthermore, a circuit layer can be formed by the following method: Before laminating the film of the present embodiment on the substrate, columnar electrodes are formed in advance on the electrode pads. After the epoxy resin composition layer is hardened, the upper surface portion of the hardened layer is ground until the columnar electrode surfaces are exposed.

[0175] When manufacturing a semiconductor package with a fan-out structure using the film of the present embodiment manufactured in the above-described manner, for example, a substrate such as a silicon wafer is diced to singulate, and each singulated piece is rearranged and fixed on a support via a film such as a die attach film, and then the film of the present embodiment is laminated from the singulated piece side and hardened to form a hardened layer. Subsequently, a redistribution layer is formed by performing an opening process, stain removal, electroless plating, and electroplating on the hardened layer, thereby obtaining a circuit layer. Further, lamination and circuit layer formation are repeated as needed, whereby a multilayer circuit can be formed. Thereafter, solder balls are arranged in a manner to achieve electrical connection with the circuit layer, whereby a package with a fan-out structure can be manufactured. Furthermore, a circuit or components and electrode pads can be formed in advance before dicing the substrate. In this case, after rearrangement to form a hardened layer, an opening can be formed in the electrode pad portion by an etching process, and a circuit layer can be formed in the opening by plating. Thereafter, a circuit pattern and electrodes are formed on the hardened layer using a photoresist material, and solder balls are arranged in a manner to achieve electrical connection with the circuit, whereby a semiconductor package with a fan-out structure can also be manufactured.

[0176] [Electronic Device] The electronic device of the present embodiment includes the printed wiring board and / or semiconductor chip package of the present embodiment described above. The printed wiring board or semiconductor wafer package of the present embodiment includes a cured product layer having low warpage, high strength, and excellent adhesion to a metal adherend. Therefore, even when it is mounted on a miniaturized, downsized, and high-density electronic device, it is possible to prevent the occurrence of connection failures or cracks due to warpage, and the obtained electronic device has excellent long-term reliability. Therefore, it is preferable.

[0177] As the electronic device, there is no particular limitation as long as it is a device that functions by incorporating electronic components. For example, examples include: various electronic devices used in electrical appliances such as computers, smartphones, game consoles, digital cameras, and televisions, transportation means such as motorcycles, automobiles, trains, ships, and airplanes, and high-speed communication antennas or servers.

[0178] The electronic device of the present embodiment can be manufactured by the following method: various semiconductor wafers are mounted on the parts where the circuit connections of the printed wiring board are made to obtain conductivity.

[0179] The method for mounting the semiconductor wafer when manufacturing the electronic device is not particularly limited. Specifically, examples include: wire bonding mounting method, flip chip mounting method, mounting method by bump-less build-up layer (BBUL), mounting method by anisotropic conductive film, mounting method by non-conductive film, etc. Further, at the time of mounting, the epoxy resin composition or film of the present embodiment can also be used for sealing, bonding, etc. of the semiconductor wafer. [Examples]

[0180] Hereinafter, the present embodiment will be described by giving specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples, and can be appropriately changed without departing from the gist of the invention.

[0181] [Preparation of epoxy resin composition] According to the blending mass fractions shown in Table 1 below, various components are respectively weighed and mixed. When the fractions shown in Table 1 below contain a solvent in each raw material, it is the non-volatile component amount after removing the solvent. For example, regarding e-1: HPC-8000-65T (toluene solution with a solid content of 65% by mass of an active ester-based curing agent, active group equivalent 223 g / eq, manufactured by DIC Corporation), when it is recorded as 30 (mass parts) in Table 1 below, it represents the non-volatile component amount, and if the solvent is included, 46.15 mass parts are added. Subsequently, a solvent adjusted to methyl ethyl ketone: cyclohexanone = 1:1 was added so that the non-volatile component ratio became 65% by mass. The formulation was stirred for 3 minutes and defoamed for 2 minutes in a non-foaming kneader placed in an environment at 25°C and mixed to obtain an epoxy resin composition for coating. The addition amount of the solvent at this time was also determined considering the amount of solvent carried by the raw materials so that the non-volatile component ratio became 65% by mass.

[0182] [Evaluation method] (Evaluation of warpage: Measurement of warpage amount) The epoxy resin composition for coating was applied to the central part of an aluminum foil with a length of 15 cm, a width of 8 cm, and a thickness of 1.7 mm so as to have a length of 12 cm, a width of 5 cm, and a dry film thickness of 150 μm, and then heated and dried in an oven preheated to 120°C for 5 minutes to obtain an aluminum foil with an epoxy resin composition layer. After the dried aluminum foil was cooled to room temperature, it was hardened in an oven at 180°C for 1 hour in a state where the four corners were fixed with heat-resistant tape to obtain an aluminum foil with a hardened product layer of the epoxy resin composition. For the aluminum foil with the hardened product layer, one end on the long side direction was fixed to a flat surface, and the height of the aluminum foil end bulging from the flat surface was measured as the warpage amount at the opposite aluminum foil end. Based on the warpage amount, evaluation was carried out according to the following criteria. <Evaluation criteria> Warpage amount: ≤5 mm 〇 5 mm < warpage amount ≤ 25 mm △ 25 mm < warpage amount ×

[0183] (Evaluation of the strength of the hardened product: Measurement of the tensile strength of the hardened product layer) After obtaining the hardened product of the epoxy resin composition by the method described in the above evaluation of warpage, the aluminum foil was peeled off and the hardened product layer was taken out. The taken-out hardened product layer was cut into a width of 5 mm and a length of 4 cm to obtain a test piece. For the cut-out specimens, a tensile test was carried out in a thermo-hygrostat at 23°C and 50% RH at a tensile speed of 100 mm / min (AUTOGRAPH AGS-X 5kN, manufactured by Shimadzu Corporation) to measure the tensile strength of the hardened layer. Based on the tensile strength, evaluation was carried out according to the following criteria. <Evaluation Criteria> Tensile strength of the hardened layer: 40 MPa or more 〇 20 MPa or more and less than 40 MPa △ Less than 20 MPa ×

[0184] (Evaluation of the bonding strength to the metal adherend: Measurement of the copper plate shear bonding strength) The above epoxy resin composition was coated on a polyethylene terephthalate film (50 μm thick) as a support so that the dry film thickness became 40 μm. Thereafter, after heating and drying in an oven preheated to 120°C for 5 minutes, the opposite side to the support was protected with a polyethylene terephthalate film subjected to easy peeling treatment to obtain a film having an epoxy resin composition layer. The above film was cut out to a size of 25 mm × 5 mm. After peeling off the protective film, it was placed and fixed together with the support between two copper plates (manufactured by Standard Testpiece Company, "C1100P"). In this state, it was heated in an oven at 60°C for 10 minutes. After the film material was transferred to the copper plate, the support was peeled off. Subsequently, again, with the epoxy resin composition layer sandwiched and fixed between two copper plates, it was heated in an oven preheated to 180°C for 1 hour to cause thermal hardening and bonding to obtain a test piece. For the obtained test piece, a tensile test was carried out in a thermo-hygrostat at 23°C and 50% RH at a tensile speed of 5 mm / min (AUTOGRAPH AGS-X 5kN, manufactured by Shimadzu Corporation) to measure the shear bonding strength (MPa). Based on the shear bonding strength, evaluation was carried out according to the following criteria. <Evaluation Criteria> Shear bonding strength: 15 MPa or more 〇 12 MPa or more and less than 15 MPa △ Less than 12 MPa ×

[0185] (Evaluation of film storage stability: Measurement of the change in the total heat of exotherm of DSC before and after film storage) By the method described in the above (evaluation of the adhesion strength to the metal adherend), a film having an epoxy resin composition layer was produced. Using a differential scanning calorimeter EXSTER7020 (manufactured by Hitachi High-Tech Science Co., Ltd.), about 10 mg of the epoxy resin composition layer was heated from 25 °C to 250 °C at a heating rate of 10 °C / min, and the total heat of exotherm was calculated from the obtained differential scanning calorimetry curve (DSC curve), and this was taken as the total heat of exotherm of the initial epoxy resin layer. Subsequently, the produced film having an epoxy resin composition layer was stored in an oven at 40 °C for 3 days. By the same measurement method as above, the total heat of exotherm of the epoxy resin composition layer after storage was calculated, and this was taken as the total heat of exotherm of the epoxy resin layer after storage. The total heat of exotherm retention rate was calculated by the following formula. Total heat of exotherm retention rate (%) = Total heat of exotherm of epoxy resin layer after storage (J / g) / Total heat of exotherm of initial epoxy resin layer (J / g) × 100 The total heat of exotherm retention rate was evaluated according to the following criteria. <Evaluation criteria> Total heat of exotherm retention rate: 95% or more 〇 90% or more and less than 95% △ Less than 90% ×

[0186] [Components of the epoxy resin composition] Hereinafter, each component in Table 1 below, which is a component used in the epoxy resin composition as an example and a comparative example, is shown.

[0187] (Component (a): Epoxy resin) · a-1: EXA850CRP (Bis A type liquid epoxy resin, epoxy equivalent 190 g / eq, manufactured by DIC Corporation) · a-2: EXA830CRP (Bis F type liquid epoxy resin, epoxy equivalent 160 g / eq, manufactured by DIC Corporation) · a-3: HP4032D (naphthalene type liquid epoxy resin, epoxy equivalent 142 g / eq, manufactured by DIC Corporation) · a-4: NC-3000 (biphenyl type solid epoxy resin, epoxy equivalent 275 g / eq, manufactured by Nippon Kayaku Co., Ltd.) · a-5: YX4000 (biphenyl type solid epoxy resin, epoxy equivalent 186 g / eq, manufactured by Mitsubishi Chemical Corporation)

[0188] (Component (b): compound represented by formula (1)) · b-1: 2-[[2-(2-hydroxyphenyl)-1H-benzimidazol-1-yl]methyl]phenol was produced by the following method. To 100 mL of dimethylformamide, 15.2 parts by mass of N,N'-bis(salicylidene)-1,2-phenylenediamine, 9.5 parts by mass of disodium sulfite, and 0.2 parts by mass of water were added, and the reaction was carried out at 80 °C for 4 hours. Then, purification was performed by silica gel column chromatography to obtain compound b-1. Compound b-1 was confirmed to be 2-[[2-(2-hydroxyphenyl)-1H-benzimidazol-1-yl]methyl]phenol by LC-MS / MS.

[0189] (Component (c): compound represented by formula (2)) · c-1: 2-(2-hydroxyphenyl)benzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0190] (Component (d): filler) · d-1: SO-E2 (spherical silica filler, average particle diameter 0.5 μm, manufactured by Admatechs Co., Ltd.)

[0191] (Component (e): specified curing agent) · e-1: HPC-8000-65T (toluene solution with 65% solid content of active ester type curing agent, active group equivalent 223 g / eq, manufactured by DIC Corporation) ·e-2: LA-3018-50P (1-methoxy-2-propanol solution containing 50% solid content of a phenolic curing agent with a tris-bonded structure, OH group equivalent 151 g / eq, manufactured by DIC Corporation)

[0192] (Component (f): polymer) f-1: PKHB (phenoxy resin, weight average molecular weight 32000, manufactured by Gabriel Phenoxies)

[0193] (Ingredient (g): Silane coupling agent) g-1: KBM-573 (aminosilane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0194] (Other ingredients) ·r-1:1B2PZ (1-benzyl-2-phenylimidazole, manufactured by SHIKOKU KASEI HOLDINGS)

[0195] [Examples 1 to 7], [Comparative Examples 1 to 2] The components were mixed in the ratios (by weight) shown in Table 1 to prepare an epoxy resin composition by the above method. The properties of the prepared epoxy resin composition were evaluated by the above method.

[0196] [Table 1] Ingredients (weight) Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Comparative example 1 Comparative example 2 a-1 5 5 5 5 5 5 5 5 5 a-2 5 5 5 5 5 5 5 5 5 a-3 5 5 5 5 5 5 5 5 5 a-4 30 30 30 30 30 30 30 30 30 a-5 10 10 10 10 10 10 10 10 10 b-1 0.15 0.03 0.15 0.03 0.15 0.0001 0.75 c-1 1 1 3 3 1 10 3 1 d-1 220 220 220 220 100 100 100 220 220 e-1 30 30 30 30 30 30 30 30 30 e-2 10 10 10 10 10 10 10 10 10 f-1 5 5 5 5 5 5 5 5 5 g-1 2.2 2.2 2.2 2.2 1 1 1 2.2 2.2 r-1 1 Total non-volatile ingredients 323.35 323.23 325.35 325.23 202.15 211.0001 204.75 323.2 323.2 Warping ○ ○ ○ ○ ○ ○ ○ ○ × Tensile strength of the cured layer ○ ○ ○ ○ ○ ○ ○ △ × Shear adhesion strength of the copper plate ○ ○ ○ ○ ○ ○ ○ × × Film storage stability ○ ○ ○ ○ ○ △ ○ △ ×

[0197] When comparing Example 1 and Comparative Example 1, it can be seen that by containing Component b-1, the cured layer has excellent tensile strength and shear adhesion strength of the copper plate, and the film has excellent storage stability when formed into a film. When comparing Example 1 and Comparative Example 2, it can be seen that by containing Components b-1 and c-1, particularly excellent low warpage properties, tensile strength of the cured product layer, and shear adhesion strength of the copper plate can be imparted. Furthermore, when made into a film, film storage stability can also be imparted.

[0198] This application is based on a Japanese patent application (Japanese Patent Application No. 2023-189603) filed with the Japan Patent Office on November 6, 2023, and its content is incorporated herein by reference. [Industrial Applicability]

[0199] The epoxy resin composition of this embodiment is excellent in low warpage properties, tensile strength of the cured product layer, and shear adhesion strength of the copper plate. When made into a film, the film storage stability is also excellent. Therefore, it has industrial applicability in the fields of sealing materials for electrical and electronic components such as underfill adhesives and relay sealing materials, various insulating liquid adhesives, die attach pastes, conductive pastes, heat-conductive pastes and other paste materials, solder resist inks, inks for via filling, resin materials such as matrix resins for fiber-reinforced plastics and impregnating and fixing materials for motor coils, or film materials such as interlayer insulating films, film-type solder resists, semiconductor package sealing sheets, die attach films, conductive films, anisotropic conductive films, non-conductive films, and heat-conductive films. In particular, in multilayer printed wiring boards, coreless substrates, and large package substrates for high-speed servers or network servers, etc., lower warpage and higher strength are further required. Therefore, the films, printed wiring boards, semiconductor chip packages, and electronic devices of the present invention can be effectively utilized.

Claims

1. A composition comprising (b): a compound represented by formula (1) below, and (c): a compound represented by formula (2) below, except for the compound represented by formula (1), and the composition being a curing agent; [Chemical 1] (in formula (1), A, B, and C are selected from any one of the group consisting of hydrogen atom, halogen atom, hydroxyl group, carboxyl group, cyano group, nitro group, alkyl group having 1 to 20 carbon atoms with substituents, alkoxy group having 1 to 20 carbon atoms with substituents, alkenyl group having 2 to 20 carbon atoms with substituents, aryl group having 6 to 20 carbon atoms with substituents, aryloxy group having 6 to 20 carbon atoms with substituents, and acetyl group having 1 to 20 carbon atoms with substituents; A, B, and C may be the same or different, and two or more A, two or more B, and two or more C may be bonded to form a monocyclic or fused ring; l, m, and n are integers from 1 to 4) [Chemical 2] (In formula (2), X is any one of 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; D and E are any one of the group consisting of hydrogen atoms, halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, alkyl groups with 1 to 20 carbon atoms that may have substituents, alkoxy groups with 1 to 20 carbon atoms that may have substituents, alkenyl groups with 2 to 20 carbon atoms that may have substituents, aryl groups with 6 to 20 carbon atoms that may have substituents, aryloxy groups with 6 to 20 carbon atoms that may have substituents, and acetyl groups with 1 to 20 carbon atoms that may have substituents; D and E may be the same or different, and two or more Ds and two or more Es may be bonded together to form a monocyclic or fused ring; o and p are integers from 1 to 4.

2. A composition comprising (b): a compound represented by formula (1) below, and (c): a compound represented by formula (2) below, except for the compound represented by formula (1), and the mass ratio of (b):(c) is (b):(c) = 0.001:100 to 20:80; [Chemical 1] (In formula (1), A, B, and C are selected from any one of the group consisting of hydrogen atoms, halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, alkyl groups with 1 to 20 carbon atoms that may have substituents, alkoxy groups with 1 to 20 carbon atoms that may have substituents, alkenyl groups with 2 to 20 carbon atoms that may have substituents, aryl groups with 6 to 20 carbon atoms that may have substituents, aryloxy groups with 6 to 20 carbon atoms that may have substituents, and acetyl groups with 1 to 20 carbon atoms that may have substituents; A, B, and C may be the same or different, and two or more A groups, two or more B groups, and two or more C groups may be bonded together to form a monocyclic or fused ring; l, m, and n are integers from 1 to 4) [Chemistry 2] In formula (2), X is any one of 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; D and E are any one of the group consisting of hydrogen atoms, halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, alkyl groups with 1 to 20 carbon atoms that may have substituents, alkoxy groups with 1 to 20 carbon atoms that may have substituents, alkenyl groups with 2 to 20 carbon atoms that may have substituents, aryl groups with 6 to 20 carbon atoms that may have substituents, aryloxy groups with 6 to 20 carbon atoms that may have substituents, and acetyl groups with 1 to 20 carbon atoms that may have substituents; D and E may be the same or different, and two or more Ds and two or more Es may be bonded together to form a monocyclic or fused ring; o and p are integers from 1 to 4.

3. The composition of claim 1 or 2, wherein in the compound represented by formula (1) above, A, B, and C are 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, 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.

4. The composition of claim 1 or 2, wherein in the compound represented by formula (2) above, X is a hydrogen atom, and D and E are 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, 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.

5. The composition of claim 1 or 2, comprising at least one selected from the group consisting of 2-[[2-(2-hydroxyphenyl)-1H-benzimidazol-1-yl]methyl]phenol, 2-[[2-(2-hydroxy-3-methoxyphenyl)-1H-benzimidazol-1-yl]methyl]-6-methoxyphenol, 2-[[2-(2-hydroxy-1-naphthyl)-1H-benzimidazol-1-yl]methyl]-1-naphthol, and 3-[[2-(2,3-dihydroxyphenyl)-1H-benzimidazol-1-yl]methyl]-1,2-benzenediol as the compound represented by formula (1) above (b).

6. The composition of claim 1 or 2, comprising at least one selected from the group consisting of 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole, 2-(1-hydroxynaphth-2-yl)benzimidazole, 2-(2-hydroxynaphth-1-yl)benzimidazole, and 2-(2-hydroxyphenyl)benzimidazole-6-carboxylic acid as the compound represented by formula (c) above: (2).

7. An epoxy resin composition comprising the composition of claim 1 or 2, and (a): epoxy resin.

8. An epoxy resin composition comprising the composition of claim 5, and (a): epoxy resin.

9. The epoxy resin composition of claim 7, further comprising (d): filler.

10. The epoxy resin composition of claim 7, further comprising (e): at least one selected from the group consisting of phenolic compounds, active ester compounds, and cyanate ester compounds.

11. The epoxy resin composition of claim 7, further comprising (f): a polymer, wherein the aforementioned components (a) and (e) are excluded.

12. The epoxy resin composition of claim 7, further comprising (g): a silane coupling agent.

13. The epoxy resin composition of claim 7, comprising, selected from 2-[[2-(2-hydroxyphenyl)-1H-benzimidazol-1-yl]methyl]phenol, 2-[[2-(2-hydroxy-3-methoxyphenyl)-1H-benzimidazol-1-yl]methyl]-6-methoxyphenol, 2-[[2-(2-hydroxy-1-naphthyl)-1H-benzimidazol-1-yl]methyl]-1-naphthol, and 3-[[2-(2,3-dihydroxyphenyl)-1H-benzimidazol-1-yl]methyl] At least one of the group consisting of 1,2-benzenediol is used as (b) above: the compound represented by formula (1), and containing at least one selected from the group consisting of 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole, 2-(1-hydroxynaphth-2-yl)benzimidazole, 2-(2-hydroxynaphth-1-yl)benzimidazole, and 2-(2-hydroxyphenyl)benzimidazole-6-carboxylic acid as (c) above: the compound represented by formula (2), The mass ratio of (b) and (c) above is (b):(c) = 0.001:100 to 20:

80. The epoxy resin composition further contains (d): filler, (e): at least one selected from the group consisting of phenolic compounds, active ester compounds, and cyanate ester compounds, (f): polymer, excluding components (a) and (e) above, and (g): silane coupling agent.

14. A membrane having a support and a resin layer on the support comprising an epoxy resin composition as claimed in any one of claims 7 to 13.

15. A printed wiring board having a cured layer of an epoxy resin composition as claimed in any one of claims 7 to 13.

16. A semiconductor wafer package having a cured layer of an epoxy resin composition as claimed in any one of claims 7 to 13.

17. An electronic device having a printed wiring board as claimed in claim 15.

18. An electronic device having a semiconductor wafer package as claimed in claim 16.