Epoxy resin composition, resin paste, film-type adhesive, printed circuit board, semiconductor chip package, and electronic device

Abstract

An epoxy resin composition comprising component (A): an epoxy resin; component (B): at least one curing agent selected from the group consisting of a phenol-based curing agent containing a triazine skeleton, an active ester-based curing agent, and a cyanate ester-based curing agent. And component (C): a compound represented by a prescribed chemical formula, preferably an imidazole compound.

Description

Technical Field

[0001] The present invention relates to an epoxy resin composition, a resin paste, a film-type adhesive, a printed circuit board, a semiconductor chip package and an electronic device. Background Art

[0002] Epoxy resins have been used in a wide range of applications, including insulating materials for semiconductor elements and other electrical and electronic components, sealing materials, adhesives, conductive materials, base resins for fiber-reinforced plastics, and impregnation and fixing agents for motor coils.

[0003] Among them, epoxy resin compositions with excellent adhesiveness and high reliability are used as adhesives for semiconductor elements and printed circuit boards. As constituent components of the epoxy resin composition, epoxy resins, curing agents such as phenolic resins reactive with the epoxy resins, and curing accelerators that accelerate the reaction between the epoxy resins and the curing agents are generally used.

[0004] In recent years, as electronic devices have become more advanced in performance, build-up layers have been used and multilayering has been achieved in electronic circuit substrate materials such as printed circuit boards, requiring miniaturization and high density of wiring, lower dielectric loss tangent for reducing transmission loss, and further requiring lower warpage of the substrate.

[0005] In addition, in the packaging of semiconductor chips obtained using the epoxy resin composition, wafer-level packaging and panel-level packaging have attracted much attention in order to achieve high productivity and low cost. For such packaging, since the epoxy resin composition is applied to a large substrate and cured, low warpage is particularly required.

[0006] Furthermore, in any application, the epoxy resin composition is similarly required to have stability during storage and rapid curing properties when heated. In addition, as the density of electronic components increases and the volume of electronic information handled increases, the heat generation of electronic devices increases, and therefore, heat resistance is also required for the epoxy resin composition.

[0007] In the past, an insulating resin material has been disclosed regarding an epoxy resin composition used as an insulating resin material for wafer-level packaging and printed circuit boards, which comprises a thermosetting resin, an inorganic filler, and a polymer resin having a glass transition temperature of 30°C or less and having one or more skeletons selected from a butadiene skeleton, a carbonate skeleton, an acrylic skeleton, and a siloxane skeleton, and further having one or more skeletons selected from an amide skeleton, an imide skeleton, and a carbamate skeleton (for example, refer to Patent Document 1). It is also disclosed that the insulating resin material has the effects of high dimensional stability and small warping by making the content of the aforementioned inorganic filler 80 to 95% by mass relative to 100% by mass of the non-volatile components of the aforementioned insulating resin material, the average particle size of the aforementioned inorganic filler being 5 μm or less, and the linear thermal expansion coefficient of the cured product of the aforementioned insulating resin material being 3 to 30 ppm / °C at 25°C to 150°C.

[0008] In addition, regarding the stability and rapid curing properties of epoxy resin compositions, a curable composition is disclosed, which includes a curing agent for anionic curable compounds formed from an imidazole-based compound having a substituted phenyl group at the 2-position of the imidazole ring (see, for example, Patent Document 2). It is also disclosed that the curable composition can selectively perform a curing reaction of the epoxy resin in a high temperature range of about 150° C. and has excellent storage stability.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent No. 7188486

[0012] Patent Document 2: Japanese Patent Application Publication No. 2016-29152 Summary of the invention

[0013] Problem that the invention aims to solve

[0014] Conventionally, the following methods have been used to reduce the warpage of substrates: introducing a soft skeleton into the molecules of resin components such as epoxy resins and polymer resins, which account for most of the epoxy resin composition, thereby alleviating the stress that causes the warpage; or by adding an inorganic filler at a high concentration to make the linear expansion coefficient of the substrate material and the epoxy resin composition close to each other, thereby suppressing the warpage.

[0015] However, as disclosed in Patent Document 1, when a predetermined amount of a polymer resin having a low glass transition temperature and a flexible skeleton is included in an epoxy resin composition, the glass transition temperature of the cured product thereof is lowered, and therefore, sufficient heat resistance cannot be obtained. In addition, when an inorganic filler is included in an epoxy resin composition at a high concentration, there are problems of limited freedom of compounding and difficulty in handling due to increased viscosity of the epoxy resin composition.

[0016] In addition, the epoxy resin composition disclosed in Patent Document 1 has a problem that there is still room for improvement in terms of achieving both stability during storage and curability during heating.

[0017] On the other hand, although the epoxy resin composition disclosed in Patent Document 2 shows that it can achieve both stability during storage and curing properties in a high temperature range of about 150°C, there is no clear indication of a composition that satisfies the physical properties such as low warpage, heat resistance, and strength required for applications such as printed circuit boards, wafer-level packaging, and panel-level packaging, and there is a problem that there is still room for research.

[0018] Therefore, in view of the above-mentioned problems of the prior art, an object of the present invention is to provide an epoxy resin composition that has a good balance between stability during storage and curability during heating, reduces warping, and exhibits high heat resistance and high strength.

[0019] Solutions for solving problems

[0020] The present inventors have conducted intensive research and have found that, as a method completely different from the conventional method of reducing warpage by adjusting the resin skeleton and the amount of inorganic filler added, by adding an imidazole compound having a specific structure as a catalyst to a specific curing agent, an epoxy resin composition can be obtained that has both stability during storage and curability during heating, reduces warpage, and can also exhibit high heat resistance and high strength, thereby completing the present invention.

[0021] That is, the present invention is as follows.

[0022] [1]

[0023] An epoxy resin composition comprising:

[0024] Component (A): epoxy resin;

[0025] Component (B): at least one curing agent selected from the group consisting of a phenolic curing agent containing a triazine skeleton, an active ester curing agent, and a cyanate curing agent; and

[0026] Component (C): a compound represented by the following formula (1) and / or a compound represented by the following formula (2).

[0027]

[0028] In formula (1) and (2), R1 and R2 are each independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent. R1 and R2 may be the same or different from each other, and R1 and R2 may be bonded to form a non-aromatic condensed ring.

[0029] 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.

[0030] Y and Z 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 optionally having a substituent, an alkoxy group having 1 to 20 carbon atoms optionally having a substituent, an alkenyl group having 2 to 20 carbon atoms optionally having a substituent, an aryl group having 6 to 20 carbon atoms optionally having a substituent, an aryloxy group having 6 to 20 carbon atoms optionally having a substituent, and an acyl group having 1 to 20 carbon atoms optionally having a substituent. Y and Z may be the same or different from each other, and two or more Ys and two or more Zs may be bonded to each other to form a monocyclic or condensed ring. m and n are integers of 1 to 4.

[0031] [2]

[0032] The epoxy resin composition according to the above [1] further comprises component (D): a filler.

[0033] 〔3〕

[0034] The epoxy resin composition according to [1] or [2], wherein in the component (C),

[0035] Y and Z are 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 with a hydroxyl group and / or a carboxyl group as a substituent, an alkoxy group having 1 to 20 carbon atoms with a hydroxyl group and / or a carboxyl group as a substituent, an aryl group having 6 to 20 carbon atoms with a hydroxyl group and / or a carboxyl group as a substituent, an aryloxy group having 6 to 20 carbon atoms with a hydroxyl group and / or a carboxyl group as a substituent, and an acyl group having 1 to 20 carbon atoms with a hydroxyl group and / or a carboxyl group as a substituent.

[0036] [4]

[0037] The epoxy resin composition according to any one of [1] to [3] above, wherein in the component (C),

[0038] The compound represented by the above formula (1) is any one selected from the group consisting of 2-(2-hydroxyphenyl)imidazole, 2-(2-hydroxyphenyl)-4(5)-methylimidazole, 4-ethyl-(2-hydroxyphenyl)-5-methylimidazole, (2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxyphenyl)-5-methylimidazole and 2-(2-hydroxy-3(5)-methoxyphenyl)imidazole,

[0039] and / or

[0040] The compound represented by the above formula (2) is 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.

[0041] 〔5〕

[0042] The epoxy resin composition according to the above-mentioned [4] further comprises component (D): a filler.

[0043] [6]

[0044] A resin paste comprising the epoxy resin composition according to any one of [1] to [5] above.

[0045] 〔7〕

[0046] A film-type adhesive having a support, and having a resin layer comprising the epoxy resin composition according to any one of [1] to [5] above on the support.

[0047] [8]

[0048] A film-type adhesive having a support, a resin layer comprising the epoxy resin composition according to any one of [1] to [5] above on the support, and a protective layer on the resin layer.

[0049] 〔9〕

[0050] A printed wiring board having a cured product layer of the epoxy resin composition according to any one of [1] to [5] above.

[0051] 〔10〕

[0052] A semiconductor chip package comprising a cured product layer of the epoxy resin composition according to any one of [1] to [5] above.

[0053]

[11]

[0054] An electronic device having the printed circuit board described in [9] above.

[0055]

[12]

[0056] An electronic device having the semiconductor chip package described in

[10] above.

[0057] Effects of the Invention

[0058] According to the present invention, it is possible to provide an epoxy resin composition that achieves both stability during storage and curability during heating, reduces warping, and exhibits high heat resistance and high strength. DETAILED DESCRIPTION

[0059] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “this embodiment”) will be described in detail.

[0060] The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented by appropriately modifying the present invention within the scope of the gist of the invention.

[0061] 〔Epoxy resin composition〕

[0062] The epoxy resin composition involved in this embodiment comprises:

[0063] Component (A): epoxy resin;

[0064] Component (B): at least one curing agent selected from the group consisting of a phenolic curing agent containing a triazine skeleton, an active ester curing agent, and a cyanate curing agent; and

[0065] Component (C): a compound represented by the following formula (1) and / or a compound represented by the following formula (2).

[0066]

[0067] In formula (1) and (2), R1 and R2 are each independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent. R1 and R2 may be the same or different from each other, and R1 and R2 may be bonded to form a non-aromatic condensed ring.

[0068] 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.

[0069] Y and Z 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 be substituted, an alkoxy group having 1 to 20 carbon atoms which may be substituted, an alkenyl group having 2 to 20 carbon atoms which may be substituted, an aryl group having 6 to 20 carbon atoms which may be substituted, an aryloxy group having 6 to 20 carbon atoms which may be substituted, and an acyl group having 1 to 20 carbon atoms which may be substituted. Y and Z may be the same or different, and two or more Ys and two or more Zs may be bonded to each other to form a monocyclic or condensed ring.

[0070] m and n are integers of 1-4.

[0071] (Component (A): epoxy resin)

[0072] The epoxy resin composition of the present embodiment contains an epoxy resin (hereinafter sometimes referred to as epoxy resin (A), component (A)).

[0073] The epoxy resin (A) is not limited to the following, and examples thereof include bifunctional epoxy resins such as 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, bixylenol 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, methylhydroquinone type epoxy resin, dibutylhydroquinone type epoxy resin, resorcinol type epoxy resin, methylresorcinol type epoxy resin, catechol type epoxy resin, and N,N-diglycidylaniline type epoxy resin.

[0074] In addition, trifunctional epoxy resins such as N,N-diglycidylaminobenzene epoxy resin, o-(N,N-diglycidylamino)toluene epoxy resin, and triazine epoxy resin can be mentioned.

[0075] Furthermore, tetrafunctional epoxy resins such as naphthalene-type tetrafunctional epoxy resins, tetraglycidyldiaminodiphenylmethane-type epoxy resins, and diaminobenzene-type epoxy resins are exemplified.

[0076] In addition, polyfunctional epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, triphenylmethane epoxy resins, tetraphenylethane epoxy resins, dicyclopentadiene epoxy resins, naphthol aralkyl epoxy resins, and brominated phenol novolac epoxy resins can be mentioned.

[0077] Furthermore, 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 ether glycol diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane diglycidyl ether, and dicyclopentadiene diglycidyl ether can be mentioned.

[0078] In addition, triepoxy resins such as trimethylolpropane triglycidyl ether and glycerol triglycidyl ether can be mentioned.

[0079] Furthermore, alicyclic epoxy resins such as vinyl (3, 4-cyclohexene) dioxide and 2- (3, 4-epoxycyclohexyl) -5, 1-spiro - (3, 4-epoxycyclohexyl) m-dioxane are mentioned.

[0080] In addition, glycidylamine type epoxy resins such as tetraglycidylbis(aminomethyl)cyclohexane are mentioned.

[0081] Furthermore, hydantoin-type epoxy resins such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin and epoxy resins having a silicone skeleton such as 1,3-bis(3-glycidyloxypropyl)-1,1,3,3-tetramethyldisiloxane are mentioned.

[0082] In addition, 2-ethylhexyl glycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, hydrogenated bisphenol A type epoxy resin, silicone-modified epoxy resin, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether , glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane diglycidyl ether, dicyclopentadiene diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, vinyl (3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane, tetraglycidyl bis(aminomethyl)cyclohexane and other glycidylamine type epoxy resins; 1,3 -Diglycidyl-5-methyl-5-ethylhydantoin epoxy resin, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane epoxy resin, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, styrene oxide, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidylphthalimide, n-butyl Aliphatic epoxy resins and alicyclic epoxy resins that can also be used as reactive diluents include 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane, 1,3-bis(3-glycidyloxypropyl)-1,1,3,3-tetramethyldisiloxane, and neodecanoic acid glycidyl ester.

[0083] The epoxy resin (A) may be solid or liquid at room temperature. As the epoxy resin (A), by including an epoxy resin that is liquid at room temperature, the stress generated can be moderately relaxed, so the epoxy resin composition of the present embodiment has a tendency to reduce warping, and can impart moderate adhesion, closeness, and flexibility when made into a film-type adhesive, so it is preferred.

[0084] Such liquid epoxy resin is not limited to the following substances, but more preferably is a liquid epoxy resin having, for example, a bisphenol A type structure, a bisphenol F type structure, a bisphenol AF type structure, a naphthalene structure, a glycidyl ester structure, a glycidyl amine structure, a phenol novolac structure, a cyclohexane structure, a cyclohexanedimethanol structure, or a butadiene structure; and an alicyclic liquid epoxy resin having an ester skeleton.

[0085] Specifically, the aforementioned liquid epoxy resins include the trade names EXA850CRP (BisA type epoxy resin), EXA830CRP (BisF type epoxy resin), HP4032, HP4032D, HP4032SS (naphthalene type epoxy resin) manufactured by DIC Corporation; the trade names jER828US, jER828EL, jER825 (bisphenol A type epoxy resin), jER807, jER1750 (bisphenol F type epoxy resin), jER152 (phenol phenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; aldehyde varnish type epoxy resin), jER630, jER630LSD (glycidylamine type epoxy resin); trade names manufactured by Nippon Steel Chemical & Materials Co., Ltd.: ZX1059 (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin); trade name manufactured by Nagase ChemteX: EX-721 (glycidyl ester type epoxy resin); trade names manufactured by Daicel: CELLOXIDE 2021P (alicyclic epoxy resin with ester skeleton), EPOLEAD PB-3600 (epoxy resin with butadiene structure); trade names manufactured by Nippon Soda Co., Ltd.: JP-100, JP-200 (epoxy resin with butadiene structure); trade name manufactured by Asahi Kasei Corporation: AER9000 (epoxy resin containing a special soft skeleton), etc.

[0086] These may be used alone or in combination of two or more.

[0087] Moreover, since the epoxy resin (A) can improve the heat resistance and the strength of the cured product layer of the epoxy resin composition of this embodiment by including a solid epoxy resin, it is preferable.

[0088] As such epoxy resins, for example, solid epoxy resins having a biphenyl structure, a bixylenol structure, a naphthalene structure, a cresol novolac structure, a dicyclopentadiene structure, a triphenol structure, a naphthol structure, a naphthyl ether structure, anthracene structure, a bisphenol A structure, a bisphenol AF structure, a tetraphenylethane structure, a bisphenol acetophenone structure, and a fluorene structure can be listed as more preferred resins.

[0089] Specifically, solid epoxy resins include the following trade names: HP-4700, HP-4710 (naphthalene-type tetrafunctional epoxy resin), N-690, N-695 (cresol novolac-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 (naphthalene ether-type epoxy resin) manufactured by DIC Corporation; the following trade names: EPPN-502H (trisphenol-type epoxy resin), NC3000, NC3000H, NC3000L, NC3100 (biphenyl-type epoxy resin), NC-7 000L (naphthol novolac type epoxy resin); Nippon Steel & Sumitomo Chemical Co., Ltd.'s trade names: ESN475V, ESN485 (naphthol type epoxy resin); Mitsubishi Chemical Co., Ltd.'s trade names: YX4000, YX4000H, YX4000HS, YL6121 (biphenyl type epoxy resin), YX4000HK (biphenylphenol type epoxy resin), YX8800 (anthracene type epoxy resin), YX7700 (novolac 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); Osaka Gas Chemical Co., Ltd.'s trade name: OGSOL PG-100, CG-500 (fluorene type epoxy resin), etc.

[0090] These may be used alone or in combination of two or more.

[0091] As the epoxy resin (A), it is preferred to use a liquid epoxy resin and a solid epoxy resin in combination from the viewpoint of being able to impart the above-mentioned effects in a well-balanced manner.

[0092] When a liquid epoxy resin and a solid epoxy resin are used in combination, the mass ratio of these (liquid epoxy resin:solid epoxy resin) is not particularly limited, but is preferably in the range of 1:0.1 to 1:6.

[0093] By setting the mass ratio of liquid epoxy resin to solid epoxy resin within the aforementioned range, the following effects can be obtained: (i) the adhesion and tightness when used in the form of a film-type adhesive are improved; (ii) when used in the form of a film-type adhesive, sufficient flexibility is obtained and the handleability is improved; and (iii) a cured product with sufficient breaking strength can be obtained, which can improve the reliability of printed circuit boards, semiconductor chip packages and electronic devices obtained using them.

[0094] From the viewpoint of the above effects (i) to (iii), the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin:solid epoxy resin) is more preferably in the range of 1:0.3 to 1:5, and even more preferably in the range of 1:0.6 to 1:4.

[0095] 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., further preferably 80 g / eq. to 2000 g / eq., further preferably 100 g / eq. to 1000 g / eq., and further preferably 120 to 900 g / eq.

[0096] When the epoxy equivalent is within the above numerical range, the crosslinking density of the cured product of the epoxy resin composition of the present embodiment becomes sufficient, and there is a tendency that a cured product layer having excellent breaking strength can be obtained.

[0097] The epoxy equivalent is the mass of a resin containing 1 equivalent of epoxy groups.

[0098] The epoxy equivalent can be measured in accordance with JIS K7236.

[0099] Regarding 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 aforementioned epoxy resin is preferably 2500 ppm or less, more preferably 2000 ppm or less, further preferably 1500 ppm or less, and further preferably 900 ppm or less.

[0100] From the viewpoint of suppressing excessive decrease, the total chlorine content in the epoxy resin (A) is preferably 0.01 ppm or more, more preferably 0.02 ppm or more, further preferably 0.05 ppm or more, further preferably 0.1 ppm or more, further preferably 0.2 ppm or more, and particularly preferably 0.5 ppm or more.

[0101] Here, the total chlorine content means the total amount of organic chlorine and inorganic chlorine contained in the epoxy resin (A), and is a mass reference value relative to the epoxy resin (A).

[0102] The total chlorine content of the epoxy resin (A) is measured by the following method.

[0103] Using xylene, the epoxy resin (A) is repeatedly washed and filtered in xylene as a washing liquid until the epoxy resin disappears. Then, the filtrate is distilled off under reduced pressure at below 100°C to obtain an epoxy resin. 1 to 10 g of the obtained epoxy resin sample is accurately weighed in a manner such that the titration amount becomes 3 to 7 mL, and dissolved in 25 mL of ethylene glycol monobutyl ether, to which 25 mL of a propylene glycol solution of 1 equivalent of KOH is added, and after boiling for 20 minutes, titrated with a silver nitrate aqueous solution, and the titration amount thus obtained is calculated.

[0104] 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, the content of the epoxy resin (A) in the total non-volatile components excluding the solvent is preferably 5% by mass or more, more preferably 7.5% by mass or more, further preferably 10% by mass or more, further preferably 12% by mass or more, and further preferably 14% by mass or more.

[0105] In addition, from the viewpoint of the handleability of the epoxy resin composition of the present embodiment and the film-type adhesive obtained using the epoxy resin composition of the present embodiment, the content of the non-volatile components is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 55% by mass or less, and further preferably 50% by mass or less.

[0106] (Component (B): specific curing agent)

[0107] The epoxy resin composition of the present embodiment contains, as a specific curing agent, at least one curing agent selected from the group consisting of phenolic curing agents containing a triazine skeleton, active ester curing agents, and cyanate curing agents (hereinafter sometimes referred to as curing agent (B), component (B)).

[0108] The phenolic curing agent containing a triazine skeleton is a curing agent that functions as a curing agent for epoxy resin and has both a triazine skeleton and a structure derived from a phenolic compound in one molecule. It is usually produced by condensing a phenolic compound with a compound having a triazine ring such as melamine or benzoguanamine and formaldehyde.

[0109] The epoxy resin composition of the present embodiment contains a phenolic curing agent containing a triazine skeleton as component (B). Therefore, the linear expansion coefficient can be suppressed low due to the triazine skeleton, so that warpage can be reduced, and heat resistance, strength, and adhesion to substrates tend to be improved.

[0110] From the viewpoint of further improving the heat resistance, strength, and adhesion to the substrate of the epoxy resin composition of this embodiment, the nitrogen content of the phenolic curing agent containing a triazine skeleton is preferably 2% by mass or more, more preferably 4% by mass or more, further preferably 5% by mass or more, further preferably 6% by mass or more, and further preferably 7% by mass or more.

[0111] On the other hand, from the viewpoint of maintaining the stability of the epoxy resin composition of the present embodiment during storage and the crosslinking density of the cured product within an appropriate range, the nitrogen content is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, further preferably 25% by mass or less, and further preferably 20% by mass or less.

[0112] In addition, from the viewpoint of further improving the crosslinking density, the phenolic curing agent containing a triazine skeleton preferably contains a phenol novolac structure. The phenolic curing agent containing a triazine skeleton containing a phenol novolac structure is not limited to the following substances, and for example, trade names such as LA3018, LA3018-50P, LA7052, LA7054, and LA1356 manufactured by DIC Corporation can be cited.

[0113] The active ester-based curing agent is a curing agent that functions as a curing agent for epoxy resin and has an active ester in the molecule.

[0114] The epoxy resin composition of this embodiment contains an active ester curing agent as component (B). Therefore, hydroxyl groups that increase the dielectric loss tangent are not generated in the epoxy resin composition due to the reaction between the active ester and the epoxy group. Therefore, there is a tendency to reduce the dielectric loss tangent.

[0115] As active ester curing agent, there is no particular limitation, and from the viewpoint of ensuring crosslinking density, it is preferably a compound having more than 2 active ester groups in 1 molecule. In addition, from the viewpoints of the heat resistance of the epoxy resin composition of the present embodiment, it is more preferably an active ester compound obtained by reacting a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound, and more preferably an active ester compound obtained by reacting a carboxylic acid compound with one or more of a phenol compound, a naphthol compound, and a thiol compound. And, it is further preferred that there are more than 2 active ester groups in 1 molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group. And, it is further preferred that the following aromatic compound: an aromatic compound obtained by reacting a compound having at least 2 or more carboxylic acids in 1 molecule with an aromatic compound having a phenolic hydroxyl group, and there are more than 2 active ester groups in 1 molecule of the aforementioned aromatic compound.

[0116] In addition, the active ester curing agent may be linear or multi-branched. In addition, if the compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, there is a tendency to improve the compatibility with the epoxy resin, and if it is a compound having an aromatic ring, there is a tendency to improve the heat resistance.

[0117] Here, examples of the carboxylic acid compound used to prepare the active ester curing agent include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. In particular, from the viewpoint of heat resistance of the epoxy resin composition of the present embodiment, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred.

[0118] Examples of the thiocarboxylic acid compound used for preparing the active ester-based curing agent include thioacetic acid and thiobenzoic acid, but are not particularly limited thereto.

[0119] Examples of the phenolic compound or naphthol compound used to prepare the active ester curing agent include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, 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, dicyclopentadienyldiphenol, and phenol novolac. Among these, from the viewpoint of heat resistance of the epoxy resin composition of the present embodiment and solubility in 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, dicyclopentadienyldiphenol, and phenol novolac are preferred, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadienyldiphenol, and phenol novolac are more preferred. Preferably, the present invention is benzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadienyl diphenol, and phenol novolac, and more preferably, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac, and more preferably, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac, and more preferably, dicyclopentadienyl diphenol and phenol novolac are used.

[0120] Examples of the thiol compound used for preparing the active ester-based curing agent include benzenedithiol and triazinedithiol, but the present invention is not particularly limited thereto.

[0121] As for the active ester compound as the active ester curing agent, the active ester compounds disclosed in Japanese Patent Application Laid-Open No. 2004-277460 and Japanese Patent Application Laid-Open No. 2013-40270 can be used, and commercially available active ester compounds can also be used. As commercially available active ester compounds, for example, trade names of DIC Corporation: EXB9451, EXB9460, EXB9460S, HPC-8000-65T (active ester compounds containing dicyclopentadiene-type diphenol structures), EXB9416-70BK (active ester compounds containing naphthalene structures), EXB9050L-62M (active ester compounds containing phosphorus atoms), trade names of Mitsubishi Chemical Corporation: DC808 (active ester compounds containing acetylated products of phenol novolac), YLH1026 (active ester compounds containing benzoylated products of phenol novolac), etc. can be cited.

[0122] The aforementioned cyanate-based curing agent refers to: function as a curing agent for epoxy resin, and has a curing agent of cyanato in the molecule. The epoxy resin composition of the present embodiment is by including a cyanate-based curing agent as component (B), thereby generating oxazoline ring, oxazolidone ring due to the reaction with an epoxy group, giving flexibility to the epoxy resin composition, and forming a triazine skeleton by the trimerization of cyanato, therefore, there is a tendency to reduce warping and especially to make good heat resistance. In addition, it is not easy to produce hydroxyl when reacting, therefore, there is a tendency that dielectric loss tangent can be suppressed to be lower.

[0123] Cyanate curing agents are not limited to the following substances, and examples thereof include novolac type (phenol novolac type, alkylphenol novolac type, etc.) cyanate resins, dicyclopentadiene type cyanate resins, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate resins, and prepolymers obtained by partially triazinizing them. Specific examples of the cyanate resin include difunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)sulfide, and bis(4-cyanatophenyl)ether; polyfunctional cyanate resins derived from phenol novolac, cresol novolac, and phenolic resins containing a dicyclopentadiene structure; and prepolymers obtained by partially triazinizing these cyanate resins.

[0124] These can be used alone or in combination of two or more.

[0125] As a commercially available cyanate ester resin, the trade name: CYTESTER (registered trademark) TA (bisphenol A type cyanate ester resin) etc. are mentioned, for example, the Mitsubishi Gas Chemical Co., Ltd.

[0126] The above-mentioned phenolic curing agent containing a triazine skeleton, active ester curing agent, and cyanate curing agent can be used alone. From the viewpoint of suppressing the dielectric loss tangent and warpage of the epoxy resin composition of this embodiment to a small level and ensuring close adhesion and adhesiveness, it is preferred to combine two or more of them. It is more preferred to combine an active ester curing agent with a phenolic curing agent containing a triazine skeleton, or a cyanate curing agent with a phenolic curing agent containing a triazine skeleton.

[0127] As described above, the mass ratio of the curing agent when two components (B) are combined is not particularly limited, and a person skilled in the art can appropriately set it according to the desired physical properties. For example, when an active ester curing agent and a phenolic curing agent containing a triazine skeleton are combined, from the viewpoint of suppressing the dielectric loss tangent and warpage of the epoxy resin composition of the present embodiment to be small and taking both adhesion and adhesiveness into consideration, the mass ratio of the non-volatile components excluding the solvent is set to 1, preferably (active ester curing agent: phenolic curing agent containing a triazine skeleton) = 1:0.05 to 1:1.5, more preferably 1:0.05 to 1:1, further preferably 1:0.07 to 1:0.8, and further preferably 1:0.1 to 1:0.6.

[0128] In addition, for example, when a cyanate curing agent and a phenolic curing agent containing a triazine skeleton are combined, from the same viewpoint as above, the mass ratio of the non-volatile components excluding the solvent is set to 1, preferably (cyanate curing agent: phenolic curing agent containing a triazine skeleton) = 1:0.05 to 1:2.0, more preferably 1:0.1 to 1:1.5, further preferably 1:0.2 to 1:1.2, and further preferably 1:0.3 to 1:1.

[0129] The content of the component (B) in the epoxy resin composition of the present 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 the components (A) and (B) to an appropriate range and preventing unreacted functional groups from remaining, the number of reactive groups of the component (B) is preferably 0.1 to 3, more preferably 0.15 to 2.5, further preferably 0.2 to 2, further preferably 0.3 to 1.8, further preferably 0.35 to 1.5, and particularly preferably 0.5 to 1.2.

[0130] Here, the "number of epoxy groups" refers to the value obtained by adding the values ​​obtained by dividing the mass of each epoxy resin present in the epoxy resin composition by the epoxy equivalent for all epoxy resins. In addition, the "reactive group" refers to a functional group that can react with an epoxy group, and for the phenolic curing agent, active ester curing agent, and cyanate curing agent containing a triazine skeleton present in the epoxy resin composition, the value obtained by adding all the values ​​obtained by dividing the mass of the non-volatile component by the reactive group equivalent.

[0131] (Component (C): a compound represented by the following formula (1) or (2))

[0132] The epoxy resin composition of the present embodiment contains a compound represented by the following formula (1) and / or a compound represented by the following formula (2) (hereinafter sometimes referred to as compound (C) or component (C)).

[0133]

[0134] In formula (1) and (2), R1 and R2 are each independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent. R1 and R2 may be the same or different from each other, and R1 and R2 may be bonded to form a non-aromatic condensed ring.

[0135] 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.

[0136] Y and Z 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 be substituted, an alkoxy group having 1 to 20 carbon atoms which may be substituted, an alkenyl group having 2 to 20 carbon atoms which may be substituted, an aryl group having 6 to 20 carbon atoms which may be substituted, an aryloxy group having 6 to 20 carbon atoms which may be substituted, and an acyl group having 1 to 20 carbon atoms which may be substituted. Y and Z may be the same or different, and two or more Ys and two or more Zs may be bonded to each other to form a monocyclic or condensed ring.

[0137] m and n are integers of 1-4.

[0138] As described above, R1 and R2 in the above general formula (1) are each independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent, or a structure in which R1 and R2 exist on the same non-aromatic condensed ring, and R1 and R2 may be the same or different from each other.

[0139] The alkyl group having 1 to 20 carbon atoms may be linear or branched, and the number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 15, and even more preferably 1 to 10. Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, isopropyl, butyl, isobutyl, hexyl, octyl, and 2-ethylhexyl.

[0140] The number of carbon atoms in the cycloalkyl group having 6 to 20 carbon atoms is preferably 6 to 18, more preferably 6 to 15. Examples of the cycloalkyl group having 6 to 20 carbon atoms include cyclohexyl, cycloheptyl, and cyclooctyl.

[0141] Specific examples of the structure in which R1 and R2 exist on the same condensed ring which does not have aromaticity include cyclopentane, cyclohexane, and dicyclopentadiene.

[0142] The aforementioned alkyl group, cycloalkyl group, and the structure in which R1 and R2 exist on the same condensed ring without aromaticity may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, and a nitro group, and a hydroxyl group and an alkoxy group are preferred.

[0143] X in the above formulae (1) and (2) 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.

[0144] The alkyl group having 1 to 20 carbon atoms as X may be linear or branched, and the number of carbon atoms in 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, isopropyl, butyl, isobutyl, hexyl, and octyl.

[0145] 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, aryl, 1-propenyl, isopropenyl, 2-butenyl, 3-butenyl, 2-pentenyl, and 2-hexenyl.

[0146] The aralkyl group having 7 to 20 carbon atoms as X 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, and naphthylmethyl.

[0147] The heteroarylalkyl group having 4 to 20 carbon atoms as X may be linear or branched, and the number of carbon atoms of the heteroarylalkyl group is preferably 4 to 18, and more preferably 4 to 15. Examples of the heteroarylalkyl group having 4 to 20 carbon atoms include triazinylmethyl, triazinylethyl, 2-pyridylmethyl, 2-pyridylethyl, 3-pyridylmethyl, 3-pyridylethyl, 4-pyridylmethyl, and 4-pyridylethyl.

[0148] In addition, the above-mentioned alkyl, alkenyl, aralkyl or heteroarylalkyl groups may each have a substituent, and examples of the substituent include a halogen atom, 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, and the like, preferably a cyano group, an alkoxy group, an amino group, an ester group, and a phenyl group.

[0149] In the above-mentioned general formulae (1) and (2), Y and Z 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 be substituted, an alkoxy group having 1 to 20 carbon atoms which may be substituted, an alkenyl group having 2 to 20 carbon atoms which may be substituted, an aryl group having 6 to 20 carbon atoms which may be substituted, an aryloxy group having 6 to 20 carbon atoms which may be substituted, and an acyl group having 1 to 20 carbon atoms which may be substituted, or are structures in which two or more Ys and two or more Zs are bonded to each other to form a monocyclic or condensed ring, and m and n are integers of 1 to 4.

[0150] The alkyl group having 1 to 20 carbon atoms as Y and Z may be linear or branched, and the number of carbon atoms in the alkyl group is preferably 1 to 18, and 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, and undecyl.

[0151] The alkoxy group having 1 to 20 carbon atoms as the aforementioned Y and Z may be linear or branched, and preferably has 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, and 2-ethylhexyloxy.

[0152] The alkenyl group having 2 to 20 carbon atoms as Y and Z may be linear or branched, and the number of carbon atoms of the alkenyl group is preferably 2 to 18, and more preferably 2 to 15. Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, aryl, 1-propenyl, isopropenyl, 2-butenyl, 3-butenyl, 2-pentenyl, and 2-hexenyl.

[0153] The carbon number of the aryl group having 6 to 20 carbon atoms as Y and Z is preferably 6 to 18, and more preferably 6 to 15. Examples of the aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, anthracenyl, and biphenylyl.

[0154] Examples of the structure in which two or more Ys or two or more Zs are bonded to form a monocyclic or condensed ring include naphthyl and anthracenyl.

[0155] The carbon number of the acyl group having 1 to 20 carbon atoms as Y and Z is preferably 1 to 18, more preferably 1 to 15. Examples of the acyl group having 1 to 20 carbon atoms include acetyl, benzoyl, and pivaloyl.

[0156] The alkyl group, alkoxy group, alkenyl group, aryl group, aryloxy group and acyl group may have a substituent, and examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, an alkoxy group, a nitro group, an ester group and a phenyl group, and preferably an alkyl group, a hydroxyl group, a carboxyl group and an alkoxy group.

[0157] Y may be a substituent at the 2-position of imidazole, i.e., any one of the ortho-position, meta-position, and para-position of the phenyl group is substituted. When there is a substituent, it is preferably substituted at a position other than the ortho-position, and further, it is preferably substituted at least at the meta-position, and it is more preferably substituted at the meta-position with a hydroxyl group or an alkoxy group having 1 to 20 carbon atoms which may have a substituent.

[0158] Among the above, Y and Z in the general formulae (1) and (2) are more preferably any 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 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.

[0159] By making Y and Z a hydrogen atom, the dielectric loss tangent of the cured product obtained by using the epoxy resin composition of this embodiment can be further reduced.

[0160] In addition, when Y and Z are hydroxyl, carboxyl, alkoxyl having 1 to 20 carbon atoms without substituent, alkyll having 1 to 20 carbon atoms with hydroxyl and / or carboxyl as substituent, alkoxyl having 1 to 20 carbon atoms with hydroxyl and / or carboxyl as substituent, aryl having 6 to 20 carbon atoms with hydroxyl and / or carboxyl as substituent, aryloxy having 6 to 20 carbon atoms with hydroxyl and / or carboxyl as substituent, or acyl having 1 to 20 carbon atoms with hydroxyl and / or carboxyl as substituent, the coordination bonding property to adherends such as metals is increased, and therefore there is a tendency to improve the adhesion and bonding strength.

[0161] The compound represented by the general formula (1) is not limited to the following, but examples thereof include the following imidazole compounds.

[0162] Examples thereof include 2-(2-hydroxyphenyl)imidazole, 2-(2-hydroxyphenyl)-4(5)-methylimidazole, 4(5)-ethyl-2-(2-hydroxyphenyl)imidazole, 4,5-dimethyl-2-(2-hydroxyphenyl)imidazole, 4-ethyl-(2-hydroxyphenyl)-5-methylimidazole, (2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxyphenyl)-5-methylimidazole, 2-(2-hydroxy-3-methylphenyl)imidazole, 2-(2-hydroxy-3-methylphenyl)-4(5)-methylimidazole, 4(5)- Ethyl-2-(2-hydroxy-3-methylphenyl)imidazole, 4,5-dimethyl-2-(2-hydroxy-3-methylphenyl)imidazole, 4-ethyl-(2-hydroxy-3-methylphenyl)-5-methylimidazole, (2-hydroxy-3-methylphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxy-3-methylphenyl)-5-methylimidazole, 2-(2-hydroxy-4-methylphenyl)imidazole, 2-(2-hydroxy-4-methylphenyl)-4(5)-methylimidazole, 4(5)-ethyl-2-(2-hydroxy-4-methylphenyl)imidazole.

[0163] In addition, 4,5-dimethyl-2-(2-hydroxy-4-methylphenyl)imidazole, 4-ethyl-(2-hydroxy-4-methylphenyl)-5-methylimidazole, (2-hydroxy-4-methylphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxy-4-methylphenyl)-5-methylimidazole, 2-(2-hydroxy-5-methylphenyl)imidazole, 2-(2-hydroxy-5-methylphenyl)-4(5)-methylimidazole, 4(5)-ethyl-2-(2-hydroxy-5-methylphenyl)imidazole, imidazole, 4,5-dimethyl-2-(2-hydroxy-5-methylphenyl)imidazole, 4-ethyl-(2-hydroxy-5-methylphenyl)-5-methylimidazole, (2-hydroxy-5-methylphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxy-5-methylphenyl)-5-methylimidazole, 2-(3-tert-butyl-2-hydroxyphenyl)imidazole, 2-(3-tert-butyl-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(3-tert-butyl-2-hydroxyphenyl)-4(5)-ethylimidazole.

[0164] Further, 2-(3-tert-butyl-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(3-tert-butyl-2-hydroxyphenyl)-4-ethyl-5-methylimidazole, 2-(3-tert-butyl-2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-2-(3-tert-butyl-2-hydroxyphenyl)-5-methylimidazole, 2-(4-fluoro-2-hydroxyphenyl)imidazole, 2-(4-fluoro-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(4-fluoro-2-hydroxyphenyl)-4( 5)-ethylimidazole, 2-(4-fluoro-2-hydroxyphenyl)-4,5-dimethylimidazole, 4-ethyl-2-(4-fluoro-2-hydroxyphenyl)-5-methylimidazole, 2-(4-fluoro-2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-2-(4-fluoro-2-hydroxyphenyl)-5-methylimidazole, 2-(4-chloro-2-hydroxyphenyl)imidazole, 2-(4-chloro-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(4-chloro-2-hydroxyphenyl)-4(5)-ethylimidazole.

[0165] In addition, 2-(4-chloro-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(4-chloro-2-hydroxyphenyl)-4-ethyl-5-methylimidazole, 2-(4-chloro-2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-2-(4-chloro-2-hydroxyphenyl)-5-methylimidazole, 2-(4-bromo-2-hydroxyphenyl)imidazole, 2-(4-bromo-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(4-chloro-2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-2-(4-chloro-2-hydroxyphenyl)-5-methylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 2-(4-chloro-2-hydroxyphenyl)-4-isopropyl-5 ...chloro-2-hydroxyphenyl)-4-isopropyl-5-methylimi imidazole, 2-(4-bromo-2-hydroxyphenyl)-4(5)-ethylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4-ethyl-5-methylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4-butyl-5-methylimidazole, 2-(2,3-dihydroxyphenyl)imidazole.

[0166] Further examples include 2-(2,3-dihydroxyphenyl)-4(5)-methylimidazole, 2-(2,3-dihydroxyphenyl)-4(5)-ethylimidazole, 2-(2,3-dihydroxyphenyl)-4,5-dimethylimidazole, 2-(2,3-dihydroxyphenyl)-4(5)-phenylimidazole, 2-(2,3-dihydroxyphenyl)-4,5-diphenylimidazole, 2-(2,5-dihydroxyphenyl)imidazole, 2-(2,5-dihydroxyphenyl)-4(5)-methylimidazole, 2-(2,5-dihydroxyphenyl)-4(5)-ethylimidazole, 2-(2,5-dihydroxyphenyl)-4,5-dimethylimidazole, 2-(2,5-dihydroxyphenyl)-4(5)-phenylimidazole, 2-(2,5 imidazole, 2-(2-hydroxy-4-methoxyphenyl)imidazole, 2-(2-hydroxy-4-methoxyphenyl)-4(5)-methylimidazole, 4(5)-ethyl-2-(2-hydroxy-4-methoxyphenyl)imidazole, 4,5-dimethyl-2-(2-hydroxy-4-methoxyphenyl)imidazole, 2-(2-hydroxy-4-methoxyphenyl)-4(5)-phenylimidazole, 4,5-diphenyl-2-(2-hydroxy-4-methoxyphenyl)imidazole, 2-(2-hydroxy-3-methoxyphenyl)imidazole, 2-(2-hydroxy-3-methoxyphenyl)-4(5)-methylimidazole, 4(5)-ethyl-2-(2-hydroxy-3-methoxyphenyl)imidazole.

[0167] Other examples include 4,5-dimethyl-2-(2-hydroxy-3-methoxyphenyl)imidazole, 2-(2-hydroxy-3-methoxyphenyl)-4(5)-phenylimidazole, 4,5-diphenyl-2-(2-hydroxy-3-methoxyphenyl)imidazole, 2-(2-hydroxy-5-methoxyphenyl)imidazole, 2-(2-hydroxy-5-methoxyphenyl)-4(5)-methylimidazole, 4(5)-ethyl-2-(2-hydroxy-5-methoxyphenyl)imidazole, 4,5-dimethyl-2-(2-hydroxy-5-methoxyphenyl)imidazole, 2-(2-hydroxy-5-methoxyphenyl)-4(5)-phenylimidazole, 4,5-diphenyl-2-(2-hydroxy-5-methoxyphenyl)imidazole, 2-(2-hydroxy-6-methoxyphenyl)imidazole, 2-(2-hydroxy-6-methoxyphenyl)-4(5)-methylimidazole, 4(5)-ethyl-2-(2-hydroxy-6-methoxyphenyl)imidazole, 4,5-dimethyl-2-(2-hydroxy-6-methoxyphenyl)imidazole, 2-(2-hydroxy-6-methoxyphenyl)-4(5)-phenylimidazole, 4,5-diphenyl-2-(2-hydroxy-6-methoxyphenyl)imidazole, 2-(3-ethoxy-2-hydroxyphenyl)imidazole, 2-(3-ethoxy-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(3-ethoxy-2-hydroxyphenyl)-4(5)-ethylimidazole, 4,5-dimethyl-2-(3-ethoxy-2-hydroxyphenyl)imidazole, 2-(3-ethoxy-2-hydroxyphenyl)-4(5)-phenylimidazole.

[0168] Further examples include 4,5-diphenyl-2-(3-ethoxy-2-hydroxyphenyl)imidazole, 2-(5-ethoxy-2-hydroxyphenyl)imidazole, 2-(5-ethoxy-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(5-ethoxy-2-hydroxyphenyl)-4(5)-ethylimidazole, 4,5-dimethyl-2-(5-ethoxy-2-hydroxyphenyl)imidazole, 2-(5-ethoxy-2-hydroxyphenyl)-4(5)-phenylimidazole, 4,5-diphenyl-2-(5-ethoxy-2-hydroxyphenyl)imidazole, 2-(4-allyl-2-hydroxyphenyl)imidazole, and 2-(4-hydroxy-2-hydroxyphenyl)imidazole. imidazole, 2-(4-allyl-2-hydroxy-3-methoxyphenyl)-4(5)-methylimidazole, 2-(4-allyl-2-hydroxy-3-methoxyphenyl)-4(5)-ethylimidazole, 2-(4-allyl-2-hydroxy-3-methoxyphenyl)-4,5-dimethylimidazole, 2-(4-allyl-2-hydroxy-3-methoxyphenyl)-4(5)-phenylimidazole, 2-(4-allyl-2-hydroxy-3-methoxyphenyl)-4,5-diphenylimidazole, 2-(4,6-dimethoxy-2-hydroxyphenyl)imidazole.

[0169] Other examples include 2-(4,6-dimethoxy-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(4,6-dimethoxy-2-hydroxyphenyl)-4(5)-ethylimidazole, 2-(4,6-dimethoxy-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(4,6-dimethoxy-2-hydroxyphenyl)-4(5)-phenylimidazole, 2-(4,6-dimethoxy-2-hydroxyphenyl)-4,5-diphenylimidazole, 2-(2-fluoro-5-hydroxyphenyl)imidazole, and 2-(2-fluoro-5- imidazole, 2-(2-fluoro-5-hydroxyphenyl)-4(5)-methylimidazole, 2-(2-fluoro-5-hydroxyphenyl)-4(5)-ethylimidazole, 2-(2-fluoro-5-hydroxyphenyl)-4,5-dimethylimidazole, 2-(2-fluoro-5-hydroxyphenyl)-4(5)-phenylimidazole, 2-(2-fluoro-5-hydroxyphenyl)-4,5-diphenylimidazole, 2-(5-fluoro-2-hydroxyphenyl)imidazole, 2-(5-fluoro-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(5-fluoro-2-hydroxyphenyl)-4(5)-ethylimidazole.

[0170] Further, 2-(5-fluoro-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(5-fluoro-2-hydroxyphenyl)-4(5)-phenylimidazole, 2-(5-fluoro-2-hydroxyphenyl)-4,5-diphenylimidazole, 2-(5-chloro-2-hydroxyphenyl)imidazole, 2-(5-chloro-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(5-chloro-2-hydroxyphenyl)-4(5)-ethylimidazole, 2-(5-chloro-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(5-chloro-2-hydroxyphenyl)-4(5)- Phenylimidazole, 2-(5-chloro-2-hydroxyphenyl)-4,5-diphenylimidazole, 2-(5-bromo-2-hydroxyphenyl)imidazole, 2-(5-bromo-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(5-bromo-2-hydroxyphenyl)-4(5)-ethylimidazole, 2-(5-bromo-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(5-bromo-2-hydroxyphenyl)-4(5)-phenylimidazole, 2-(5-bromo-2-hydroxyphenyl)-4,5-diphenylimidazole, 2-(6-fluoro-2-hydroxy-3-methoxyphenyl)imidazole.

[0171] In addition, 2-(6-fluoro-2-hydroxy-3-methoxyphenyl)-4(5)-methylimidazole, 2-(6-fluoro-2-hydroxy-3-methoxyphenyl)-4(5)-ethylimidazole, 2-(6-fluoro-2-hydroxy-3-methoxyphenyl)-4,5-dimethylimidazole, 2-(6-fluoro-2-hydroxy-3-methoxyphenyl)-4(5)-phenylimidazole, 2-(6-fluoro-2-hydroxy-3-methoxyphenyl)-4,5-diphenylimidazole, 2-(1-hydroxynaphthalen-2-yl)imidazole, 2-(1-hydroxynaphthalen-2-yl)-4(5)-methylimidazole, 2-(1-hydroxynaphthalen-2-yl)-4 (5)-ethylimidazole, 4,5-dimethyl-2-(1-hydroxynaphthalene-2-yl)imidazole, 2-(1-hydroxynaphthalene-2-yl)-4(5)-phenylimidazole, 4,5-diphenyl-2-(1-hydroxynaphthalene-2-yl)imidazole, 2-(2-hydroxynaphthalene-1-yl)imidazole, 2-(2-hydroxynaphthalene-1-yl)-4(5)-methylimidazole, 2-(2-hydroxynaphthalene-1-yl)-4(5)-ethylimidazole, 4,5-dimethyl-2-(2-hydroxynaphthalene-1-yl)imidazole, 2-(2-hydroxynaphthalene-1-yl)-4(5)-phenylimidazole, 4,5-diphenyl-2-(2-hydroxynaphthalene-1-yl)imidazole, and the like.

[0172] The compound represented by the general formula (2) is not limited to the following, but examples thereof include the following imidazole compounds.

[0173] Examples thereof 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, and 2-(2-hydroxy-5-methoxyphenyl)benzimidazole. imidazole, 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 and the like.

[0174] Among these, from the viewpoint of being able to obtain a uniform epoxy resin composition due to excellent solubility in the epoxy resin (A) and the solvent and achieving both reduced warpage of the cured product and high heat resistance, as the compound represented by the aforementioned general formula (1), it is preferred that both R1 and R2 are hydrogen atoms or have different substituents, for example, more preferably 2-(2-hydroxyphenyl)imidazole, 2-(2-hydroxyphenyl)-4(5)-methylimidazole, 4-ethyl-(2-hydroxyphenyl)-5-methylimidazole, (2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxyphenyl)-5-methylimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)imidazole, and even more preferably 2-(2-hydroxyphenyl)imidazole.

[0175] In addition, from the viewpoint of obtaining the same effect, the compound represented by the aforementioned general formula (2) is preferably 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole, 2-(1-hydroxynaphthalene-2-yl)benzimidazole, 2-(2-hydroxynaphthalene-1-yl)benzimidazole, and 2-(2-hydroxyphenyl)benzimidazole-6-carboxylic acid, and more preferably 2-(2-hydroxyphenyl)benzimidazole and 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole.

[0176] The epoxy resin composition of the present embodiment comprises component (C): the compound represented by the general formula (1) and (2) as a catalyst, and surprisingly, the warpage of the cured product can be reduced and high heat resistance can be imparted. This effect cannot be easily inferred from the structure of component (C). Furthermore, the inventors have verified the effect of imidazole compounds having various structures in the process of realizing the present invention, but the compound that can reduce the warpage of the cured product and also impart high heat resistance is limited to the case where the component (C) of the present invention is used as a catalyst, which is an extremely special effect.

[0177] In addition, component (C) is a component that catalytically reacts with component (A): epoxy resin, and the above-mentioned effect can be exhibited simply by adding it to the epoxy resin composition. Therefore, unlike the previous method of reducing warpage, the following effect can be obtained: there is no need to mix epoxy resins or polymers with soft skeletons or mix fillers at high concentrations, and the effect of reducing warpage can be achieved, which can greatly increase the mixing freedom of technicians in this field.

[0178] In the epoxy resin composition of the present embodiment, by adding the compound of the above-mentioned component (C) to the above-mentioned specific curing agent (component (B)), not only stability and curability can be achieved, but also the warpage of the cured product can be reduced and high heat resistance can be exhibited. The following reasons are considered, but it is not intended to be limited to the following mechanism.

[0179] Component (C) has a structural feature that a hydroxyphenyl group is substituted at the 2-position of imidazole relative to an imidazole structure that reacts with an epoxy group. As described in Patent Document 2, in order to balance stability and curability, it is believed that the nucleophilicity of nitrogen on imidazole is suppressed and stabilized during storage by forming an intramolecular hydrogen bond between nitrogen at the reaction site of imidazole and the adjacent hydroxyphenyl group, but the hydrogen bond dissociates and reacts when heated.

[0180] Next, with regard to reducing the warpage and high heat resistance of the cured product, the results of the study on various imidazole compounds confirm that the component (C) used in the epoxy resin composition of the present embodiment has observed a significant effect. It can be considered that: component (C) due to its structural characteristics, exerts the adjacent hydroxyphenyl to epoxy group and imidazole to react and open the ring when the anion produced to supply protons to achieve stabilization as a chain transfer agent. Therefore, during the polymerization reaction, the generation of rapid high molecular weight bodies concentrated around the reaction site and local thickening can be suppressed, and chain extension reaction can occur in the system as a whole. Therefore, it can be considered that: by gently and evenly occurring thickening during curing and easily easing the stress generated during curing, the warpage in the cured product is reduced, and in addition, unreacted epoxy groups are not easy to remain, therefore, a high crosslinking density is presented, and high heat resistance is presented.

[0181] Furthermore, for the above-mentioned specific curing agent (component (B)), when the compound of the above-mentioned component (C) is used as a catalyst, the above-mentioned effect can be further obtained. For example, due to their structure, phenolic curing agents and cyanate curing agents containing a triazine skeleton tend to have deteriorated storage stability due to the presence of amine groups and cyanato groups that react with epoxy groups even in the absence of a catalyst. When a catalyst is added, the degree of deterioration becomes more significant. In addition, the active ester curing agent has low reactivity to react directly with epoxy groups. Therefore, it is important to add a catalyst and cure at a high temperature of more than 180°C for the performance of physical properties, but general catalysts will competitively cause self-polymerization of epoxy groups before the active esters fully react at the curing temperature, so unreacted active ester groups are likely to remain.

[0182] On the other hand, if it is the above-mentioned component (C), due to its structure, even when using a phenolic curing agent or a cyanate curing agent containing a triazine skeleton, the storage stability can be greatly improved. In addition, when reacting at a high temperature such as above 150°C or above 180°C, the rapid self-polymerization reaction of the epoxy group itself can be suppressed by the function as a chain transfer agent, and the reaction of each curing agent (B) with the epoxy group can be efficiently carried out. Therefore, the unreacted functional group is not easy to remain, and there is a tendency to give full play to the original heat resistance and strength of the composition. In addition, component (C) uniformly catalyzes the reaction of the curing agent (B) with the epoxy group, so that the stress will not be locally concentrated during curing, and the effect of reducing the warping of the cured product can be further shown.

[0183] In view of the above mechanism, as long as the component (C) has the structural characteristics represented by the general formula (1) and / or (2), it can be used in combination with a wide range of curing agents (B), including those having various substitutions on the functional groups, to achieve the effects of the present invention.

[0184] Since the component (C) has an aromatic ring and a hydroxyl group, it has excellent compatibility with resins having an aromatic ring and polar solvents and can be well dissolved in various epoxy resins and solvents.

[0185] Generally speaking, as imidazole compounds with high stability, solid dispersion type imidazole compounds with reduced compatibility with epoxy resins are known, but such imidazole compounds are solid, so there is a concern that the uniformity of curing is reduced. In addition, especially in the case of a process of thin film formation with a blending solvent such as a film-type adhesive, there are the following problems: the film-forming property is reduced due to residual particles, and it cannot be applied to an extremely thin film. Depending on the type of solvent, even a solid dispersion type is dissolved without showing stability, etc. Therefore, a component (C) used in the epoxy resin composition of the present embodiment that can be uniformly dissolved in a resin and a solvent and has both stability and reactivity is suitable for applications using solvents such as film-type adhesives.

[0186] In the epoxy resin composition of the present embodiment, the mass ratio of the above-mentioned component (B) to the component (C) is not particularly limited. For the mass ratio of the non-volatile components excluding the solvent, taking the component (B) as 100, it is preferably (component (B): component (C)) = 100:0.1 to 100:40, more preferably 100:0.5 to 100:30, further preferably 100:1 to 100:20, further preferably 100:1.5 to 100:15, further preferably 100:1.8 to 100:12, and particularly preferably 100:2 to 100:10.

[0187] By adopting this range, the effect of promoting the reaction of component (B) achieved by component (C) can be fully obtained, and the excess self-polymerization reaction of the epoxy resin caused by component (C) can be prevented, and the crosslinking density of the obtained cured product is within an appropriate range. Therefore, there is a tendency to obtain a cured product layer with better heat resistance and strength.

[0188] In addition, the content of component (C) in the epoxy resin composition as a whole of the present embodiment is not particularly limited. From the viewpoint of obtaining sufficient curability, in all non-volatile components excluding solvents, it is preferably 0.005% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, further preferably 0.15% by mass or more, and further preferably 0.2% by mass or more. In addition, from the viewpoint of appropriately maintaining the curing speed and maintaining the uniformity of the cured layer, it is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 4% by mass or less, further preferably 3% by mass or less, and further preferably 2% by mass or less. Wherein, component (C) and component (A): epoxy resin undergo catalytic reaction, therefore, those skilled in the art can set an appropriate amount considering the materials, composition, and desired performance used.

[0189] (Ingredient (D): filler)

[0190] The epoxy resin composition of the present embodiment may further contain a filler (hereinafter sometimes referred to as filler (D) or component (D)).

[0191] The filler (D) is not particularly limited, and examples thereof include one or more selected from the group consisting of an inorganic filler (inorganic filler) from the viewpoint of reducing warpage, an inorganic filler obtained by pre-treating an inorganic filler with a silane coupling agent (H) described later, and an organic filler from the viewpoint of improving bonding strength and crack resistance.

[0192] These may be used alone or in combination of two or more.

[0193] The shape of the filler (D) is not particularly limited, and may be, for example, an irregular shape, a spherical shape, or a scaly shape.

[0194] From the viewpoint of making the linear expansion coefficients of the epoxy resin composition of the present embodiment close to those of the adherend substrate and reducing warpage, it is preferred that an inorganic filler is contained.

[0195] Inorganic fillers are not limited to the following substances, and examples thereof include, but are not limited to, ceramics such as silica, alumina, glass, cordierite, organic silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, 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, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate; carbons such as carbon nanotubes and graphene; metals or alloys such as gold, silver, copper, nickel, aluminum, zinc, tin, lead, solder, indium and palladium; particles obtained by covering a polymer nucleating material with a metal film, etc.

[0196] Among these, from the viewpoint of further reducing the warpage of the cured product, it is preferred to include silicon dioxide. As silicon dioxide, for example, amorphous silicon dioxide, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be listed, and from the viewpoint of making the filling property and the handling property of the epoxy resin composition good, its shape is more preferably spherical.

[0197] Examples of commercially available spherical fused silica include trade names SO-C2, SO-C1, SO-E2, and SO-E1 manufactured by ADMATECHS.

[0198] The average particle size of the filler (D) is not particularly limited, but 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, from the viewpoint of forming a cured layer using the epoxy resin composition containing the aforementioned component (D) and being able to form fine wiring on the aforementioned cured layer.

[0199] On the other hand, when an epoxy resin composition is used to form a resin paste, as a moderate viscosity, from the viewpoint of making a resin paste with good handleability, the average particle size of component (D): filler is preferably 0.01 μm or more, more preferably 0.03 μm or more, further preferably 0.05 μm or more, 0.07 μm or more, or 0.1 μm or more.

[0200] The average particle size of the filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the filler can be prepared according to the volume basis by using a laser diffraction particle size distribution measuring device, and the median particle size can be used as the average particle size for measurement. As a laser diffraction particle size distribution measuring device, a trade name of HELOS manufactured by Sympatec can be used.

[0201] When an inorganic filler is used as the filler (D), 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. It is preferably 5 to 98% by mass, more preferably 10 to 95% by mass, further preferably 15 to 90% by mass, further preferably 20 to 88% by mass, further preferably 25 to 85% by mass, and particularly preferably 30 to 80% by mass, based on the total non-volatile components excluding the solvent.

[0202] By setting the range, the epoxy resin composition and film-type adhesive of the present embodiment can further exhibit the following effects (i) to (iii): (i) being able to maintain appropriate viscosity and having excellent handling properties; (ii) the resin component and the inorganic filler are within a range that is neither too much nor too little, and having excellent adhesion, close fit, and dimensional stability; (iii) having excellent warping, heat resistance, and breaking strength when the resin composition is cured.

[0203] The organic filler is a filler having a function as an impact-resistant moderating agent having stress relaxation properties. The epoxy resin composition of the present embodiment contains an organic filler, thereby tending to further improve the adhesion to various connecting members and suppress the generation and aggravation of fillet cracks.

[0204] The aforementioned organic filler is not limited to the following substances, and examples thereof include, but are not particularly limited to, acrylic resins, silicone resins, butadiene rubber, polyester, polyurethane, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic rubber, polystyrene, acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), silicone-modified resins, and organic microparticles of copolymers containing these as components.

[0205] From the viewpoint of improving adhesion, the organic particles are preferably, for example, alkyl (meth)acrylate-butadiene-styrene copolymers, alkyl (meth)acrylate-silicone copolymers, silicone-(meth)acrylic copolymers, composites of silicone and (meth)acrylic acid, composites of alkyl (meth)acrylate-butadiene-styrene and silicone, and composites of alkyl (meth)acrylate and silicone.

[0206] As the organic filler, organic fine particles having a core-shell structure and having a core layer and a shell layer with different compositions may be used.

[0207] Examples of core-shell type organic fine particles include particles having a silicone-acrylic rubber as a core and an acrylic resin grafted thereto, and particles having an acrylic copolymer grafted thereto and an acrylic resin grafted thereto, but are not particularly limited thereto.

[0208] The low elastic modulus achieved by the inclusion of core-shell organic fine particles reduces the stress generated in the fillet portion, and there is a tendency to suppress the generation of fillet cracks. In addition, when fillet cracks are generated, the contained core-shell organic fine particles act as a stress relaxant, and there is a tendency to suppress the aggravation of fillet cracks.

[0209] As the constituent material of the core layer, a material with excellent flexibility is preferably used. As the constituent material of the core layer, it is not limited to the following substances, and examples thereof include silicone elastomers, butadiene elastomers, styrene elastomers, acrylic elastomers, polyolefin elastomers, and silicone / acrylic composite elastomers.

[0210] On the other hand, as the constituent material of the shell layer, it is preferred that the material has excellent affinity for other components such as semiconductor resin sealing materials, especially for epoxy resin. As the constituent material of the shell layer, for example, acrylic resin and epoxy resin can be listed, but they are not particularly limited to them. Among these, acrylic resin is particularly preferred from the viewpoint of affinity for other components such as semiconductor resin sealing materials, especially for epoxy resin.

[0211] When an organic filler is used 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. It is preferably 1 to 20% by mass, more preferably 2 to 18% by mass, and further preferably 3 to 16% by mass relative to the total amount of the epoxy resin composition.

[0212] When the content of the organic filler is 1% by mass or more, a stress relaxation function is exhibited, and there is a tendency that an effect of improving adhesive strength can be obtained.

[0213] When the content of the organic filler is 20% by mass or less, there is a tendency that the effect of heat reflow resistance can be obtained.

[0214] (Component (E): solvent)

[0215] The epoxy resin composition of the present embodiment may further contain a solvent (hereinafter sometimes referred to as a solvent (E) or a component (E)).

[0216] By including the solvent (E), there is a tendency to make the compound of the component (C) more uniformly compatible in the epoxy resin composition. Thus, the curing uniformity of the cured layer formed by the epoxy resin composition of this embodiment can be improved. In addition, by using the solvent (E) and selecting the component (C) having various structures according to the desired reaction temperature range and reaction speed, there is a tendency to further exhibit performance such as reduced warping and high heat resistance.

[0217] The solvent (E) is not particularly limited, and a known solvent can be used.

[0218] The solvent (E) is not limited to the following substances, and examples thereof include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and solvent naphtha; ketones such as acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and acetophenone; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ethyl ether acetate, and γ-butyrolactone; alcohols such as methanol, ethanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol, 2-phenoxyethanol, and 1-methoxy-2-propanol; and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0219] These may be used alone or in combination of two or more.

[0220] The content of the solvent (E) in the epoxy resin composition of the present embodiment is not particularly limited. When the epoxy resin composition is used in the form of a varnish or a paste by mixing with a solvent, the content of the solvent (E) is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, further preferably 15 to 70% by mass, further preferably 20 to 65% by mass, and further preferably 25 to 60% by mass, based on the entire epoxy resin composition, from the viewpoint of uniformly dissolving various components and controlling the viscosity to an appropriate range to improve handling properties.

[0221] In addition, when other components contain solvents, such as when component (B) contains a solvent as a solvent, the above content also includes these solvents and is a preferred range of the ratio of the solvent in the entire epoxy resin composition.

[0222] In addition, the content of the solvent (E) when the epoxy resin composition of the present embodiment is made into a film-type adhesive is not particularly limited. From the viewpoint of suppressing the generation of bubbles, it is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 6% by mass or less relative to the entire epoxy resin composition. On the other hand, from the viewpoint of preventing the adhesion and flexibility of the film-type adhesive from being reduced due to excessive reduction of the solvent, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.1% by mass or more relative to the entire epoxy resin composition.

[0223] (Component (F): other curing agent)

[0224] The epoxy resin composition of the present embodiment may further contain a curing agent (hereinafter sometimes referred to as curing agent (F) or component (F)) other than the above-mentioned component (B): the prescribed curing agent (B) and component (C): the compound of the general formula (1) or (2).

[0225] As component (F), any curing agent known in the art for use in epoxy resins can be widely used without particular limitation, and examples thereof include amine curing agents, amide curing agents, phenolic curing agents (excluding phenolic curing agents containing a triazine skeleton), acid anhydride curing agents, imidazole curing agents (excluding component (C)), carbodiimide curing agents, benzoxazine curing agents, phosphorus curing agents, thiol curing agents, catalyst-type curing agents, and modified products thereof.

[0226] These may be used alone or in combination of two or more.

[0227] The amine curing agent is not limited to the following, and examples thereof include aliphatic amines, aromatic amines, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0228] Examples of the aliphatic amine include, but are not limited to, triethylamine, tributylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, meta-xylylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornene diamine, and 1,2-diaminocyclohexane.

[0229] Examples of the aromatic amine include, but are not limited to, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), polytetramethylene oxide-diparaaminobenzoate, KAYAHARD AA manufactured by Nippon Kayaku Co., Ltd., and ETHACURE 100 manufactured by MITSUI FINE CHEMICALS, INC.

[0230] Examples of the amide curing agent include, but are not limited to, dicyandiamide and guanidine compounds as derivatives thereof, compounds obtained by adding an acid anhydride to an amine curing agent, and hydrazide compounds.

[0231] Examples of the hydrazide curing agent containing a hydrazide compound include, but are not limited to, succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, p-hydroxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide, and maleic acid dihydrazide.

[0232] The guanidine curing agent containing a guanidine compound is not limited to the following substances, and examples thereof include dicyandiamide, dicyandiamide-aniline adducts, dicyandiamide-methylaniline adducts, dicyandiamide-diaminodiphenylmethane adducts, dicyandiamide-diaminodiphenyl ether adducts and other dicyandiamide derivatives; guanidine salts such as guanidine nitrate, guanidine carbonate, guanidine phosphate, guanidine sulfamate, and aminoguanidine hydrogen carbonate; methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, cyclohexylguanidine, phenylguanidine, diphenylguanidine, toluoylguanidine, acetylguanidine, diacetylguanidine, propionylguanidine, di Propionylguanidine, cyanoacetylguanidine, guanidine succinate, diethylcyanoacetylguanidine, guanyl urea, N-oxymethyl-N'-cyanoguanidine, N,N'-diethoxycarbonylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, 1-(o-tolyl)biguanidine, etc.

[0233] The phenolic curing agent (excluding phenolic curing agents containing a triazine skeleton) is not limited to the following substances, and examples thereof include phenol novolac resin, bisphenol A novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol-phenol co-condensation novolac resin, naphthol-cresol co-condensation novolac resin, allyl acrylic phenolic resin, phenolic resin containing a dicyclopentadiene skeleton, phenolic resin containing a biphenyl skeleton, phenolic resin containing a naphthalene skeleton, and the like.

[0234] As commercially available phenolic curing agents, for example, there are the following: TD2090 (phenol novolac resin), EXB-9500 (phenolic resin containing a naphthalene skeleton) manufactured by DIC Corporation; the following: HF-1M (phenol novolac resin), MEH-7700, MEH-7810, MEH-7851 (phenolic resin containing a biphenyl skeleton) manufactured by UBE Corporation; the following: NHN, CBN, GPH (phenolic resin containing a naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd.; the following: SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (phenolic resin containing a naphthalene skeleton) manufactured by Nippon Steel Chemical & Materials Co., Ltd.

[0235] Among these, from the viewpoint of improving the heat resistance and strength of the cured product, preferably, a phenolic curing agent containing a bisphenol A type structure, a bisphenol F type structure, a bisphenol AF type structure, a naphthalene structure, a phenol novolac structure, a cyclohexane structure, a cyclohexanedimethanol structure, a butadiene structure, a biphenyl type structure, a bixylenol structure, a cresol novolac structure, a dicyclopentadiene structure, a triphenol structure, a naphthol structure, a naphthyl ether structure, anthracene structure, a tetraphenylethane structure, a bisphenol acetophenone structure, or a fluorene structure.

[0236] Examples of the acid anhydride curing agent include, but are not limited to, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0237] Examples of the imidazole curing agent other than the component (C) include, but are not limited to, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4- diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and the like.

[0238] The carbodiimide curing agent is not limited to the following substances, and examples thereof include trade names of Carbodilite V-02B, V-03, V-04K, V-07, and V-09 manufactured by Nisshinbo Chemical Co., Ltd., and trade names of Stabaxol P, P400, and Hycasyl 510 manufactured by Rhein Chemie Co., Ltd. In addition, modified products of carbodiimide compounds such as those disclosed in Japanese Patent No. 7226954 may also be used.

[0239] The benzoxazine-based curing agent is not limited to the following, and examples thereof include HFB2006M (trade name) manufactured by Showa Highpolymer Co., Ltd. and Pd, Fa, and ALP-d (trade names) manufactured by Shikoku Chemical Holdings Co., Ltd.

[0240] Examples of the phosphorus-based curing agent include, but are not limited to, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate.

[0241] As the thiol curing agent, it is not limited to the following substances as long as it contains two or more thiol groups in one molecule, and examples thereof include 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetra(thioglycolate), ethylene glycol dimercaptoacetate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)ethyl]-isocyanurate, 1,3,5-tris(3-mercaptopropionyloxy)ethyl]-isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexa(3-mercaptopropionate), 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluril, 4-butanedithiol, 1,6-hexaneedithiol, 1,10-decanedithiol, etc. From the viewpoint of 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, pentaerythritoltetrakis(3-mercaptopropionate), and pentaerythritoltetrakis(3-mercaptobutyrate) are preferred. From the viewpoint of low-temperature curability of the epoxy resin composition of the present embodiment, pentaerythritoltetrakis(3-mercaptopropionate) and pentaerythritoltetrakis(3-mercaptobutyrate) are more preferred.

[0242] The catalyst type curing agent is not limited to the following, and examples thereof include a cationic heat curing catalyst and a BF3-amine complex.

[0243] The curing agent as a modified product is not limited to the following substances, and examples thereof include polyamine compounds, amine-epoxy adducts, amine-urea adducts, imidazole-epoxy adducts, amine imide compounds, or microcapsule-type curing agents formed by covering them, curing agents formed by adsorbing them to porous bodies, etc. As specific examples thereof, but not limited to the following substances, the following trade names can be listed: NOVACURE HX-3722, HX-3742, HX-3088, HX-3613, HXA3932HP, HXA9322HP, HXA9382HP, HXA9192HP manufactured by Asahi Chemical Industry Co., Ltd.; the trade names of Ajinomoto Fine Science Co., Ltd.: AMICURE PN-23J, PN-40J, MY-24; the trade names of Fuji Chemical Industry Co., Ltd.: FUJICURE FXR-1020, FXR-1030, etc.

[0244] Among the above, as component (F), for example, from the viewpoint of improving the adhesion between the epoxy resin composition of the present embodiment and the substrate material or reacting with various active hydrogen groups to increase the crosslinking density and fully exhibit the strength of the cured product, it is preferred to include a carbodiimide-based curing agent. In addition, from the viewpoint of obtaining a cured product with high dimensional stability, high flame retardancy, low dielectric loss tangent, and low water absorption, it is preferred to include a benzoxazine-based curing agent.

[0245] The content of component (F) in the epoxy resin composition of the present embodiment can be appropriately set according to the reactivity and expected performance of the above-mentioned components (B) and (C), and is not particularly limited. From the viewpoint of obtaining good reactivity, in all non-volatile components excluding solvent, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 1.0% by mass or more. In addition, from the viewpoint of obtaining good storage stability, it is preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.

[0246] (Component (G): thermoplastic resin)

[0247] The epoxy resin composition of the present embodiment may further contain a thermoplastic resin (hereinafter sometimes referred to as thermoplastic resin (G) or component (G)).

[0248] By including the thermoplastic resin (G), when the epoxy resin composition of the present embodiment is cast or applied to a predetermined thickness and dried to be molded into a film, cracks and fissures can be prevented and the film shape can be maintained.

[0249] Thermoplastic resins (G) are not limited to the following substances, and examples thereof include phenoxy resins, polyvinyl acetal resins, vinyl resins containing acid anhydride groups, polyolefin resins, polybutadiene resins, polyimide resins, polyamide-imide resins, styrene-based elastomer resins, polyether sulfone resins, polyphenylene ether resins, polysulfone resins, and acrylic resins.

[0250] The thermoplastic resin (G) may be used alone or in combination of two or more.

[0251] From the viewpoint of obtaining a cured product layer with sufficient strength using the epoxy resin composition of the present embodiment, the weight average molecular weight of the thermoplastic resin (G) is preferably 10,000 or more, more preferably 15,000 or more, further preferably 20,000 or more, further preferably 25,000 or more, and further preferably 30,000 or more. From the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the thermoplastic resin (G) is preferably 200,000 or less, more preferably 180,000 or less, further preferably 160,000 or less, and further preferably 150,000 or less. The weight average molecular weight of the thermoplastic resin (G) can be measured using, for example, a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight (in terms of polystyrene) of the thermoplastic resin can be measured at a column temperature of 40° C. using HLC-8320GPC manufactured by Tosoh Corporation as a measuring apparatus, using Shodex KF-804 / KF-803 / KF-802 / KF-802 manufactured by Resonac as a column, using tetrahydrofuran or the like as a mobile phase, and calculating using a calibration curve of standard polystyrene.

[0252] From the viewpoint of improving the crosslinking density of the cured product of the epoxy resin composition of the present embodiment, making the heat resistance and strength of the cured product layer sufficient, the thermoplastic resin (G) preferably has a functional group comprising one or more atoms or carbon-carbon double bonds selected from the group consisting of oxygen atoms, nitrogen atoms and sulfur atoms. As the functional group, one or more selected from the group consisting of hydroxyl, carboxyl, anhydride, epoxy, amino, thiol, enol, enamine, urea, cyanate, isocyanate, thioisocyanate, imide, alkenyl, allenyl and ketone groups can be listed. As anhydride, preferably carboxylic anhydride. As a suitable example of alkenyl, vinyl, allyl, styryl can be listed. When the thermoplastic resin contains the functional group, the functional group equivalent of the thermoplastic resin (G) 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 functional group equivalent is not particularly limited, and can usually be 50 or more, 100 or more, etc.

[0253] A suitable thermoplastic resin (G) will be described in more detail below. However, a thermoplastic resin obtained by further adding the above-mentioned functional group to the thermoplastic resin shown below according to a known procedure can also be suitably used as the component (G).

[0254] As suitable phenoxy resins, for example, phenoxy resins 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 listed, and the terminal of the phenoxy resin can be any functional group such as a phenolic hydroxyl group and an epoxy group.

[0255] Specific examples of phenoxy resins include: 1256, 4250 (phenoxy resins containing a bisphenol A skeleton), YX8100 (phenoxy resins containing a bisphenol S skeleton), YX6954, YX6954BH30 (phenoxy resins containing a bisphenol acetophenone skeleton), YX7553, YX7553BH30 (phenoxy resins containing a biscresol fluorenone skeleton), YL6794 (phenoxy resins containing a terpene skeleton), YL7213, YL7290 (phenoxy resins containing a trimethylcyclohexane skeleton), YL7500BH30, YL7769BH30, YL7482 manufactured by Mitsubishi Chemical Corporation; and FX280, FX293 (phenoxy resins containing a bisphenol fluorenone skeleton) manufactured by Nippon Steel Chemicals & Materials Co., Ltd.

[0256] Specific examples of the polyvinyl acetal resin include Denka Butyral 4000-2, 5000-A, 6000-C, and 6000-EP manufactured by Denkagaku Kogyo Co., Ltd. and S-LEC BH series, BX series, KS series (eg, KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

[0257] As the vinyl resin containing anhydride groups, for example, copolymers of monomers (d1) containing anhydride groups and other monomers (d2) can be listed. As the monomers (d1) containing anhydride groups, for example, maleic anhydride, itaconic anhydride, citraconic anhydride, and aconitic anhydride can be listed. As other monomers (d2), there is no particular limitation as long as they can copolymerize with the monomers (d1) containing anhydride groups, and for example, ethylenically unsaturated monomers such as (meth)acrylic acid, (meth)acrylate, and styrene can be listed. As specific examples of vinyl resins containing anhydride groups, trade names manufactured by Cray Valley Company: EF-30, EF-40, EF-60, and EF-80 can be listed.

[0258] Specific examples of the polyimide resin include RIKACOAT SN-20 and PN-20 (trade names: Shin Nippon Chemical Co., Ltd.) and UNIDIC V-8000 (trade name: DIC Corporation).

[0259] Specific examples of polyimide resins include linear polyimides obtained by reacting difunctional hydroxy-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (Japanese Patent Publication No. 2006-37083); polyimides containing a polysiloxane skeleton (Japanese Patent Publication No. 2002-12667, Japanese Patent Publication No. 2000-319386, International Publication No. 2010 / 53186, etc.); and the like.

[0260] Specific examples of the polyamide-imide resin include VYLOMAX HR11NN and HR16NN (trade names) manufactured by Toyobo Co., Ltd. and HPC-5020, HPC-6000, HPC-7200 and HPC-9000 (trade names) manufactured by Resonac Co., Ltd.

[0261] As styrene-based elastomer resins, for example, block copolymers containing a block of styrene or its analog as at least one terminal block and an elastomer block of a conjugated diene or its hydrogenate as at least one middle block can be cited. Specifically, styrene-butadiene diblock copolymers, styrene-butadiene triblock copolymers, styrene-isoprene diblock copolymers, styrene-isoprene triblock copolymers, hydrogen-added styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene triblock copolymers, hydrogenated styrene-isoprene diblock copolymers, hydrogenated styrene-isoprene triblock copolymers, hydrogenated styrene-butadiene random copolymers, etc. can be cited. As specific examples of styrene-based elastomer resins, trade names manufactured by Asahi Kasei Corporation: ASAPRENE, TUFPRENE, ASAFLEX; trade names manufactured by Kuraray: HYBRAR, SEPTON.

[0262] Specific examples of the polyethersulfone resin include PES5003P (trade name) manufactured by Sumitomo Chemical Co., Ltd., and the like.

[0263] Specific examples of the polysulfone resin include trade names: polysulfone P1700 and P3500 manufactured by Solvay Advanced Polymers.

[0264] Specific examples of the polybutadiene resin include G-1000, G-3000, GI-1000, and GI-3000 manufactured by Nippon Soda Co., Ltd.; R-45EPI manufactured by Idemitsu Petrochemical Co., Ltd.; Epofriend AT501 manufactured by Daicel Corporation; and Ricon 130, Ricon 142, Ricon 150, Ricon 657, and Ricon 130MA manufactured by Cray Valley Corporation.

[0265] Specific examples of the acrylic resin include SG-P3, SG-600LB, SG-280, SG-790, and SG-K2 manufactured by Nagase ChemteX Co., Ltd. and SN-50, AS-3000E, and ME-2000 manufactured by Negami Industries, Ltd.

[0266] Among them, from the viewpoint of ensuring sufficient heat resistance and strength of the cured product layer obtained using the epoxy resin composition of this embodiment, ensuring long-term connection reliability, and appropriately maintaining compatibility with the epoxy resin (A) and ensuring curing uniformity, the thermoplastic resin (G) preferably contains one or more selected from the group consisting of phenoxy resins, polyvinyl acetal resins, vinyl resins containing acid anhydride groups, polyimide resins, polyamide-imide resins, styrene-based elastomer resins and acrylic resins.

[0267] In addition, regarding the epoxy resin composition of the present embodiment, when applied to materials such as flexible wiring boards that are bent and assembled into electronic devices, by containing a thermoplastic resin (G), it is possible to achieve low elasticity of the cured layer of the epoxy resin composition, and it is possible to suppress breaking and peeling. If it is such a use requiring low elasticity, as a thermoplastic resin (G), it is not limited to the following substances. For example, if it contains a resin having one or more structures selected from polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure and polycarbonate structure in the molecule, it is easy to obtain the effect of low elasticity, which is suitable. In addition, even if it contains a thermoplastic resin having a glass transition temperature of less than 25°C or a liquid at 25°C, it can also be used appropriately from the viewpoint of obtaining the same effect of low elasticity.

[0268] The content of the thermoplastic resin (G) in the epoxy resin composition of the present embodiment can be appropriately set according to the epoxy resin (A), curing agent (B), the content of other curing agents and their types, and the content of filler (D), the desired performance of the epoxy resin composition of the present embodiment, and is not particularly limited. From the viewpoint of ensuring the adhesion and flexibility of the epoxy resin composition of the present embodiment, in all non-volatile components excluding solvents, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 1.2% by mass or more, and further preferably 1.5% by mass or more. From the viewpoint of keeping the heat resistance and strength of the epoxy resin composition of the present embodiment well, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and further preferably 20% by mass or less.

[0269] (Component (H): silane coupling agent)

[0270] The epoxy resin composition of the present embodiment may further contain a silane coupling agent (hereinafter sometimes referred to as a silane coupling agent (H) or a component (H)).

[0271] By including the silane coupling agent (H), the affinity between the resin component and the filler or between the resin component and the adherend substrate can be improved, and the uniform dispersibility of the filler component tends to be improved, and the adhesiveness of the epoxy resin composition tends to be improved, which is preferred.

[0272] In the present embodiment, the silane coupling agent (H) is contained, which 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 of the following methods (i) to (iii).

[0273] Method (i):

[0274] A method in which the filler (D) is treated with a silane coupling agent in advance and the treated filler is blended into the epoxy resin composition.

[0275] Method (ii):

[0276] Method for directly adding silane coupling agent to epoxy resin composition (integral blending method)

[0277] Method (iii):

[0278] A method of mixing the epoxy resin (A) and the thermoplastic resin (G) used in the form of a silylated resin such as a resin obtained by copolymerizing a monomer with a silane coupling agent by reacting the silane coupling agent with the resin terminal or side chain.

[0279] The above methods (i) to (iii) are all acceptable. If it is (i), it is preferred from the viewpoint that the alcohol that becomes a by-product of the silane coupling reaction is not easy to remain in the system and the viewpoint that the dispersibility of the filler is better. If it is (ii) or (iii), it is preferred from the viewpoint that affinity can be exerted between the resin and the filler as well as between the resin and the adhered substrate, which can make the adhesion and tightness better.

[0280] The silane coupling agent (H) is a substance having at least one hydrolyzable group such as an alkoxy group or an aryloxy group bonded to a silicon atom, and may further have an alkyl group, an alkenyl group, or an aryl group bonded thereto. In addition, the alkyl group may be a group substituted with an amino group, an alkoxy group, an epoxy group, or a (meth)acryloyloxy group.

[0281] The silane coupling agent (H) is not limited to the following, but preferably contains one or more silane coupling agents selected from the group consisting of, for example, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, styrylsilane coupling agents, acrylate silane coupling agents, isocyanate silane coupling agents, sulfide silane coupling agents, vinyl silane coupling agents, silane coupling agents, organosilazane compounds and titanate coupling agents from the viewpoint of improving the uniform dispersibility of the filler component and improving the adhesiveness and close adhesion of the resin composition.

[0282] Specific examples of the silane coupling agent (H) include aminosilane 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; 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, Epoxysilane coupling agents such as 3-glycidyloxypropyl (dimethoxy) methyl silane, glycidylbutyl trimethoxysilane, and 2-(3,4-epoxycyclohexyl) ethyl trimethoxysilane; mercaptosilane coupling agents such as 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl methyl dimethoxysilane, and 11-mercapto undecyl trimethoxysilane; styrene silane coupling agents such as p-styrene trimethoxysilane; 3-acryloxypropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl dimethoxysilane, 3- Acrylate silane coupling agents such as methacryloxypropyl triethoxysilane and 3-methacryloxypropyl diethoxysilane; isocyanate silane coupling agents such as 3-isocyanate propyl trimethoxysilane; sulfide silane coupling agents such as bis(triethoxysilylpropyl) disulfide and bis(triethoxysilylpropyl) tetrasulfide; silane coupling agents such as methyl trimethoxysilane, octadecyl trimethoxysilane, phenyl trimethoxysilane, methacryloxypropyl trimethoxysilane, imidazole silane, triazine silane, tert-butyl trimethoxysilane; 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 and other organosilazane compounds;Titanium tetrabutyl ester dimer, isopropoxy octyl glycolate titanium, titanium tetrabutyl ester, titanium octyl glycolate, diisopropyl bis(triethanolamine) titanate, dihydroxy bis(lactate) titanium dihydroxy complex, bis(dioctyl pyrophosphate) ethylene titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, tri-n-butoxy monostearate titanium, titanium tetrabutyl ester, titanium tetra(2-ethylhexyl) ester, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diene Titanate coupling agents such as propyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumylphenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearyl diacryloyl titanate, isopropyl dimethacryloyl isostearyl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tri(dodecylbenzenesulfonyl) titanate, isopropyl tri(dioctyl pyrophosphate) titanate, and isopropyl tri(N-amidoethyl-aminoethyl) titanate. ;

[0283] Among these, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, and organosilazane compounds are preferred, and aminosilane coupling agents are more preferred.

[0284] Examples of commercially available products include trade names such as KBM403 (3-glycidoxypropyltrimethoxysilane), KBM803 (3-mercaptopropyltrimethoxysilane), KBE903 (3-aminopropyltriethoxysilane), KBM573 (N-phenyl-3-aminopropyltrimethoxysilane), and SZ-31 (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0285] The content of the silane coupling agent (H) in the epoxy resin composition of the present embodiment is not particularly limited, but is preferably 0.1 to 2.0 parts by mass relative to 100 parts by mass of the filler (D), from the viewpoint of improving the dispersibility of the filler (D), the adhesiveness and close adhesion of the epoxy resin composition of the present embodiment, and suppressing excessive side reactions.

[0286] (additive)

[0287] The epoxy resin composition of the present embodiment may contain, in addition to the above-mentioned components (A) to (H), additives such as diluents, reactive diluents, pigments, dyes, flow regulators, thickeners, reinforcing agents, release agents, wetting agents, flame retardants, surfactants, stabilizers, and adhesion aids as necessary.

[0288] The diluent is not limited to the following, and examples thereof include dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and the like.

[0289] The reactive diluent is a compound having a reactive functional group such as an epoxy group or an acryloyl group that can be incorporated into a cured structure, and is a compound that has an effect of reducing the viscosity of the epoxy resin composition by being added to the epoxy resin composition of the present embodiment.

[0290] The reactive diluent is not limited to the following, and examples thereof include acrylate compounds and epoxy compounds that can reduce the viscosity without impairing the reactivity.

[0291] The acrylate compound used as the reactive diluent is not limited to the following substances, and examples thereof include 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 multifunctional (meth)acrylate, pentaerythritol type multifunctional (meth)acrylate, dipentaerythritol type multifunctional (meth)acrylate, and the like.

[0292] The epoxy compound used as the reactive diluent is not limited to the following substances, and examples thereof include n-butyl glycidyl ether, tert-butyl glycidyl ether, diglycidyl aniline, N,N′-glycidyl o-toluidine, phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether.

[0293] It should be noted that various monoepoxy compounds and glycidyl ether compounds of polyols can also be used as reactive diluents, but these compounds have only one functional group (epoxy group, glycidyl group) in one molecule that helps to react with component (B), component (C) and component (F). Although they volatilize and do not cause pores, they cannot form three-dimensional crosslinks during curing, so there is a tendency that the heat resistance and toughness of the cured product of the epoxy resin composition cannot be sufficient. Therefore, as a reactive diluent, from the viewpoint of being able to form three-dimensional crosslinks during curing and suppressing the decrease in heat resistance and toughness during curing, it is preferably a compound containing two or more glycidyl groups in one molecule.

[0294] In addition, the reactive diluent may be used individually by 1 type, or may use 2 or more types together.

[0295] The content of reactive diluent can be appropriately set according to the desired performance of the epoxy resin composition of the present embodiment, is not particularly limited, and is preferably 1.0 mass parts or more and 30 mass parts or less relative to 100 mass parts of epoxy resin (A). By making the content more than 1.0 mass parts, there is a tendency that the viscosity rise of the epoxy resin composition of the present embodiment at room temperature can be suppressed, and the embedding property can be suppressed when used as a wiring embedding film. In addition, there is a tendency that the heat resistance and toughness during curing can be suppressed, and the generation and aggravation of fillet cracks can be suppressed. On the other hand, by making the content of reactive diluent less than 30 mass parts relative to 100 mass parts of epoxy resin (A), there is a tendency to suppress the reduction of adhesion and the peeling during the moisture absorption reflow test. For the purpose of suppressing the viscosity rise that occurs when a large amount of fillers (D) are filled, it is also preferred to also contain reactive diluent.

[0296] Examples of the pigment include, but are not limited to, kaolin, chalk powder, gypsum, antimony trioxide, PENTON, aerosol, lithopone, barite, and titanium dioxide.

[0297] Examples of the dye include, but are not limited to, natural dyes such as dyes derived from plants such as madder and indigo, and dyes derived from minerals such as loess and laterite; synthetic dyes such as alizarin and indigo; and fluorescent dyes.

[0298] Examples of the flow control agent include, but are not limited to, organic titanium compounds such as titanium tetraisopropoxide and titanium diisopropoxybis(acetylacetonate); and organic zirconium compounds such as zirconium tetra-n-butoxide and zirconium tetraacetylacetonate.

[0299] The thickener is not limited to the following substances, and examples thereof include animal thickeners such as gelatin; plant thickeners such as polysaccharides and cellulose; chemically synthesized thickeners such as polyacrylic acid, modified polyacrylic acid, polyether, urethane-modified polyether, and carboxymethyl cellulose.

[0300] Examples of reinforcing agents include, but are not limited to, polyethylene sulfone powders such as "SUMIKA EXCELPES" manufactured by Sumitomo Chemical Co., Ltd., nano-sized functional group-modified core-shell rubber particles such as "KANEACE MX" manufactured by Kaneka Co., Ltd., and silicone-based reinforcing agents such as polyorganosiloxane.

[0301] Examples of the release agent include, but are not limited to, fluorine-based release agents, silicone-based release agents, and acrylic-based release agents composed of a copolymer of glycidyl (meth)acrylate and a linear alkyl (meth)acrylate having 16 to 22 carbon atoms.

[0302] The wetting agent is not limited to the following, and examples thereof include unsaturated polyester copolymer-based wetting agents having an acidic group such as acryl polyphosphate.

[0303] The flame retardant is not limited to the following, and examples thereof include bromine-based flame retardants, phosphorus-based flame retardants, and inorganic flame retardants.

[0304] Examples of the bromine-based flame retardant include tetrabromophenol, but are not particularly limited thereto.

[0305] Examples of the phosphorus-based flame retardant include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and epoxy derivatives thereof, triphenylphosphine or derivatives thereof, phosphoric acid esters, condensed phosphoric acid esters, and phosphazene compounds, but are not particularly limited thereto.

[0306] Examples of the nitrogen-based flame retardant include melamine polyphosphate, isocyanuric acid, guanidine-based flame retardants, and triazine-based flame retardants, but are not particularly limited thereto.

[0307] Examples of the inorganic flame retardant compound include magnesium hydroxide and aluminum hydroxide, but are not particularly limited thereto.

[0308] From the viewpoint of heat resistance, phosphazene compounds and magnesium hydroxide are preferred. In addition, phosphazene compounds disclosed in Japanese Patent No. 723041 can also be used.

[0309] In addition, the flame retardant may be used individually by 1 type, or may use 2 or more types together.

[0310] The content of the flame retardant is not particularly limited, but is preferably 5.0 parts by mass or more and 200 parts by mass or less, and more preferably 10 parts by mass or more and 100 parts by mass or less, based on the mass (100 parts by mass) of the epoxy resin (A).

[0311] The surfactant is not limited to the following substances, and examples thereof include anionic surfactants such as alkylbenzene sulfonates and alkyl polyoxyethylene sulfates; cationic surfactants such as alkyl dimethyl ammonium salts; amphoteric surfactants such as alkyl dimethyl amine oxides and alkyl carboxy betaines; nonionic surfactants such as linear alcohols having 25 or more carbon atoms and fatty acid esters, etc.

[0312] As a stabilizer, as a substance that improves the storage stability of the epoxy resin composition, for example, boric acid and cyclic borate compounds, isocyanuric acid, barbituric acid, aluminum chelating agents, etc. can be suitably used, but are not particularly limited thereto. A cyclic borate compound refers to a compound containing boron in a cyclic structure. From the viewpoint of compatibility with the resin and uniformity of curing, the cyclic borate compound is preferably 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborane).

[0313] In addition, the stabilizer may be used alone or in combination of two or more.

[0314] As adhesion aids, any component added for the purpose of forming a coordination bond with a metal or substrate material and improving affinity can be widely used. From the viewpoint of forming a good coating on the adherend surface and further obtaining the effect of improving adhesion, thiazole compounds and triazole compounds are preferred.

[0315] The additives may be added in an amount appropriate in terms of function, for example, pigments and / or dyes may be added in an amount that can impart a desired color to the epoxy resin composition of the present embodiment. In addition, those skilled in the art may appropriately set an appropriate amount of addition according to the content of the compounding and the desired performance.

[0316] [Epoxy resin composition, and resin paste obtained using the same]

[0317] The epoxy resin composition of the present embodiment and the resin paste obtained using the same can be obtained by containing the above-mentioned components (A) to (C), and adding components (D) to (H) and the above-mentioned additives as needed and mixing them.

[0318] That is, the resin paste of this embodiment contains the epoxy resin composition of this embodiment.

[0319] The mixing method is not particularly limited, and methods known to those skilled in the art can be used. It is not limited to the following method, and can be obtained by fully mixing until uniformity using, for example, an open roll such as a three-roll mill, a dissolver, a planetary stirrer, a rotary stirrer, a kneader, an extruder, etc.

[0320] (Specific aspects of epoxy resin composition and resin paste obtained using the same)

[0321] The epoxy resin composition of this embodiment has excellent low warpage, high heat resistance and high strength while taking into account both stability and reactivity. Therefore, it can be used as a sealing material for electrical and electronic components such as relay sealing materials; various insulating liquid adhesives, mold adhesive pastes, conductive pastes, thermal conductive pastes and other paste materials; ink materials such as solder mask inks and hole filling inks; base resins for fiber reinforced plastics, impregnation fixing materials for motor coils, etc.

[0322] In particular, solvents are mostly added to paste materials and ink materials. If the epoxy resin composition of this embodiment contains component (C), component (C) is uniformly dissolved in the solvent. Therefore, no particles remain when the paste or ink is applied / filled, and a cured product with high curing uniformity can be obtained. Therefore, it has excellent strength and long-term durability and is more suitable.

[0323] Low warpage, high heat resistance, and high strength are also common properties required for other liquid adhesives, base resins for fiber-reinforced plastics, and impregnation fixing materials for motor coils. Therefore, the epoxy resin composition of this embodiment meets these requirements and is suitable for any form.

[0324] 〔Film-type adhesive〕

[0325] The epoxy resin composition of this embodiment can be made into a film-type adhesive.

[0326] The film-type adhesive of the present embodiment includes, for example, a predetermined support and a resin layer composed of the epoxy resin composition of the present embodiment, and may include a protective layer on the surface of the resin layer opposite to the support, if necessary.

[0327] (Supporting body)

[0328] The support constituting the film-type adhesive is preferably made of a material that can withstand the temperature at which the solvent is dried.

[0329] Such a support is not limited to the following substances, and examples thereof include 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, and cellulose derivative film.

[0330] As these films, stretched films may be used as necessary.

[0331] (Protective layer)

[0332] The protective layer is preferably made of a material that can sufficiently maintain the surface smoothness of the resin layer constituting the film-type adhesive.

[0333] Such a protective layer is not limited to the following protective layers, and preferably, a polyethylene film, a polypropylene film, a polyethylene terephthalate film subjected to an easy-peeling treatment, an oriented polypropylene film, or the like can be used.

[0334] (Method for producing film-type adhesive)

[0335] The film-type adhesive of the present embodiment can be produced by laminating a support, a resin layer, and, if necessary, a protective layer in this order.

[0336] As a method for laminating the support, the resin layer, and the protective layer, a known method can be adopted.

[0337] For example, the epoxy resin composition of the present embodiment to which the solvent (E) is added is prepared. First, it is applied to the support using a known method such as an applicator, a rod coater, a lip coater, a die coater, a roller coater, a blade coater, etc., and dried to form a resin layer on the support. There is no particular limitation on the drying method, and examples thereof include an oven, hot air blowing, etc. In addition, there is no particular limitation on the drying temperature and time. From the viewpoint of fully removing the solvent and suppressing the deformation of the support caused by excessive heating and the excess reaction of the resin layer during drying, it is preferably dried within a temperature range of 50°C to 160°C and within a drying time of 1 minute to 30 minutes, and more preferably dried at 80°C to 150°C for 3 minutes to 25 minutes. It should be noted that the drying temperature may be a constant temperature or a temperature gradient may be applied. Then, as required, a film-type adhesive can be manufactured by laminating a protective layer on the formed resin layer.

[0338] (Specific form of film-type adhesive)

[0339] The film-type adhesive of this embodiment is not limited to the following substances, and can be used as, for example, interlayer insulating films, film-type solder resists, sealing sheets for semiconductor packages, mold adhesive films, conductive films, anisotropic conductive films, non-conductive films, thermal conductive films, etc.

[0340] The film-type adhesive obtained by using the epoxy resin composition of this embodiment not only has various stabilities required in the manufacture of film-type adhesives, such as stability during varnish storage until coating and drying, stability at drying temperature, and film storage stability, but also has low warping, heat resistance, and strength of the cured layer. Therefore, it is particularly effective for materials such as film-type adhesives that are prone to warping and must ensure high strength and reliability in the thin cured layer. In addition, component (C) will be uniformly dissolved in the epoxy resin composition or solvent, so the surface smoothness of the film-type adhesive of this embodiment is excellent and can also be closely attached to the substrate without gaps.

[0341] The above-mentioned properties are the common properties required by interlayer insulating films, film-type solder resists, sealing sheets for semiconductor packages, mold adhesive films, conductive films, anisotropic conductive films, non-conductive films, thermal conductive films, etc. Therefore, the film-type adhesive of this embodiment is suitable for these methods.

[0342] 〔Printed circuit board〕

[0343] The printed wiring board of the present embodiment has a cured product layer of the epoxy resin composition of the present embodiment.

[0344] When the film-type adhesive of the present embodiment is used to manufacture a printed circuit board, the film-type adhesive manufactured by the above method is pasted to the inner layer circuit substrate processed by the pattern, and laminated while pressing and heating from the side of the support. The surface of the inner layer circuit can be roughened in advance. Lamination is carried out at normal pressure or reduced pressure using an intermittent method or a continuous method based on a roller, and preferably both sides are laminated at the same time. The lamination conditions at this time are preferably: the crimping temperature is 70°C to 150°C and the crimping pressure is 0.1 to 1MPa. In addition, in order to prevent the formation of voids, lamination is preferably carried out under a reduced pressure of less than 2KPa. After lamination, after cooling to room temperature, the support film is peeled off, and the adhesive film laminated on the inner layer circuit substrate is heated and cured to form a cured layer. As curing conditions, it is preferred that the curing temperature is 130 to 200°C and the curing time is in the range of 30 minutes to 120 minutes.

[0345] Next, after the through-holes are opened using a laser such as a carbon dioxide laser, the roughening treatment is performed using an oxidant such as permanganate, dichromate, and ozone for the purpose of removing dirt and improving the adhesion to the plating layer. Thereafter, a conductor circuit is selectively formed on the cured layer by electroless plating and electrolytic plating, and a conductor is formed on the inner wall of the through-hole, thereby forming an outer layer circuit. Thereafter, an annealing treatment is performed at 150 to 200°C for 30 to 60 minutes, thereby improving the adhesion between the conductor layer and the resin layer. On the conductor circuit layer obtained by the above operation, a film-type adhesive is further used to repeat the above manufacturing method, thereby forming a multi-stage build-up layer and manufacturing a printed circuit board.

[0346] As described above, the cured product of the epoxy resin composition of the present embodiment has little warpage, high heat resistance, and high strength, and therefore can be widely used in printed circuit boards such as rigid substrates, flexible substrates, single-sided laminated substrates, and thin substrates, and can be particularly suitably used as a build-up layer of a multilayer printed circuit board.

[0347] 〔Semiconductor chip package〕

[0348] The semiconductor chip package of the present embodiment has a cured product layer of the epoxy resin composition of the present embodiment.

[0349] By using the film-type adhesive of this embodiment, a semiconductor chip package with low warpage, excellent heat resistance and strength can be produced. In particular, it can be suitably used in wafer-level packaging and panel-level packaging where low warpage becomes important due to the use of a large-area substrate. The film-type adhesive can be laminated on both sides of the substrate used, or on a single side. Various considerations have been made for the method of manufacturing the package, which can be roughly divided into a fan-in structure and a fan-out structure.

[0350] When a semiconductor chip package of a fan-in structure is manufactured using the film-type adhesive manufactured by the above operation, for example, the film-type adhesive manufactured by the above method is laminated on a substrate such as a silicon wafer having a circuit, a component, and an electrode pad and cured to obtain a cured product layer. The lamination conditions and curing conditions at this time may be the same as those when manufacturing a printed circuit board, or may be appropriately changed according to the heat resistance of the component used.

[0351] Next, a rewiring layer is formed on the cured layer by hole opening, dirt removal, electroless plating and electrolytic plating, thereby obtaining a circuit layer. Furthermore, a multilayer circuit can be formed by repeatedly laminating and forming a circuit layer as needed. Thereafter, solder balls are arranged in a manner that is connected to the circuit layer, and dicing is performed to achieve singulation, thereby manufacturing a semiconductor chip package of a fan-in structure in the present invention.

[0352] It should be noted that before laminating the film-type adhesive layer on the substrate, a columnar electrode is formed on the electrode pad in advance, and after the film-type adhesive is cured, the upper surface of the cured layer is polished until the columnar electrode surface is exposed, thereby forming a circuit layer.

[0353] When a semiconductor chip package with a fan-out structure is manufactured using the film-type adhesive manufactured as described above, for example, a substrate such as a silicon wafer is cut into individual pieces, and the individual pieces are reconfigured / fixed on a support body with the aid of a film such as a mold adhesive film, and then the film-type adhesive of this embodiment is stacked from the single piece side and cured to form a cured layer.

[0354] Next, a rewiring layer is formed on the solidified layer by hole opening, dirt removal, electroless plating and electrolytic plating, thereby obtaining a circuit layer. Furthermore, a multi-layer circuit can be formed by repeatedly laminating and forming a circuit layer as needed. Thereafter, a semiconductor chip package with a fan-out structure can be manufactured by arranging solder balls in a manner that is conductive with the circuit layer.

[0355] It should be noted that before cutting the substrate, the circuit, components, and electrode pads can be preformed. In this case, after rearrangement to form a solidified layer, an opening can be formed in the electrode pad portion by etching, and a circuit layer can be formed in the opening by plating. Thereafter, a circuit pattern and electrodes are formed on the solidified layer using a photoresist material, and solder balls are arranged in a manner that is conductive with the circuit, thereby also being able to manufacture a semiconductor chip package with a fan-out structure.

[0356] 〔Electronic devices〕

[0357] The electronic device of the present embodiment includes the printed circuit board and / or the semiconductor chip package of the present embodiment described above.

[0358] The printed circuit board and semiconductor chip package of this embodiment have a low-warping, high-heat-resistant, and high-strength cured layer. Therefore, even when installed in a miniaturized, miniaturized, and high-density electronic device, it is possible to prevent poor connection and cracking caused by warping, and it is also possible to achieve durability against heat release associated with the large-capacity electronic information being processed. Therefore, the long-term reliability of the resulting electronic device becomes excellent, so it is preferred.

[0359] The electronic device is not particularly limited as long as it is a device that is assembled with electronic components to perform functions, and examples thereof include electronic products such as personal computers, smart phones, game consoles, digital cameras and televisions, transportation vehicles such as motorcycles, cars, trains, ships and airplanes, and various electronic devices used in high-speed communication antennas, servers, etc.

[0360] The electronic device of this embodiment can be manufactured by mounting various semiconductor chips on the portions of the printed circuit board where circuit connection is to be performed and achieving conduction.

[0361] There is no particular limitation on the method for mounting the semiconductor chip when manufacturing the electronic device of this embodiment. Specifically, there can be listed a wire bonding mounting method, a flip chip mounting method, a mounting method based on a built-in non-bump layer (BBUL), a mounting method based on anisotropic conductive film, a mounting method based on non-conductive film, etc.

[0362] In addition, during packaging, the epoxy resin composition of this embodiment and a resin paste or film-type adhesive obtained using the epoxy resin composition can be used to perform sealing, bonding, and the like of semiconductor chips.

[0363] Example

[0364] Hereinafter, the present embodiment will be described with reference to specific examples and comparative examples. However, the present invention is not limited to the following examples and comparative examples, and can be modified appropriately within the scope of the present invention.

[0365] In addition, unless otherwise specified, the "parts" and "%" below are based on mass.

[0366] [Preparation of epoxy resin composition]

[0367] Each component was weighed so as to have the compounding number shown in the components of the following Tables 1 to 3, and was fully mixed until it was uniform, thereby obtaining an epoxy resin composition.

[0368] In addition, in the table, when the product used later contains a solvent, the component (B) is described as the number of parts including the solvent.

[0369] [Measurement and evaluation methods of characteristics]

[0370] (Evaluation of varnish storage stability: Measurement of varnish thickening ratio)

[0371] The viscosity of the epoxy resin composition immediately after preparation (initial viscosity) and the viscosity of the epoxy resin composition after storage at 25° C. for 2 weeks were measured at room temperature (25° C.) using an E-type viscometer (TVE-35H, manufactured by Toki Sangyo Co., Ltd.), and the varnish thickening ratio was calculated according to the following mathematical formula (1).

[0372] Varnish thickening ratio (times) = viscosity after storage at 25°C for 2 weeks / initial viscosity ... mathematical formula (1)

[0373] The thickening ratio is evaluated as preferably 1.5 times or less, more preferably 1.2 times or less, further preferably 1.1 times or less, and further preferably 1.0 times.

[0374] In addition, in the following Tables 1 to 3, the case where the epoxy resin composition after storage thickened significantly and the viscosity could not be measured was described as gelation.

[0375] (Evaluation of curability: Appearance inspection)

[0376] The prepared epoxy resin composition was used to apply an epoxy resin composition layer to the central portion of an aluminum foil having a length of 15 cm, a width of 8 cm, and a thickness of 1.7 mm so that the length became 12 cm, the width became 5 cm, and the dry film thickness became 150 μm. The epoxy resin composition was then heated and dried in an oven preheated to 120° C. for 5 minutes to obtain a thin film.

[0377] After the dried film was naturally cooled to room temperature, it was cured in an oven at 150°C for 1 hour for Examples 1 to 6 and Comparative Examples 1 and 2, and in an oven at 180°C for 1 hour for other Examples and Comparative Examples, with the four corners fixed with heat-resistant tape, to obtain a cured layer.

[0378] For the cured material layer after curing, if a uniform cured material layer with no stickiness on the surface and cross section and no parts with different color tones can be obtained, the curability is evaluated as good and expressed as 0.

[0379] (Evaluation of warpage: Measurement of warpage amount)

[0380] The prepared epoxy resin composition was used to apply an epoxy resin composition layer to the central portion of an aluminum foil having a length of 15 cm, a width of 8 cm, and a thickness of 1.7 mm so that the length became 12 cm, the width became 5 cm, and the dry film thickness became 150 μm. The epoxy resin composition was then heated and dried in an oven preheated to 120° C. for 5 minutes to obtain a thin film.

[0381] After the dried film was naturally cooled to room temperature, it was cured in an oven at 150°C for 1 hour for Examples 1 to 6 and Comparative Examples 1 and 2, and in an oven at 180°C for 1 hour for other Examples and Comparative Examples, with the four corners fixed with heat-resistant tape, to obtain a cured product.

[0382] One end of the cured aluminum foil was fixed to a flat surface along the longitudinal direction, and the height of the other end of the aluminum foil from the flat surface was measured as the warpage amount.

[0383] Evaluation was performed based on the warpage amount according to the following criteria.

[0384] <Evaluation Criteria>

[0385] Warpage ≤5mm…◎◎

[0386] 5mm<Warp≤10mm…◎

[0387] 10mm<Warp≤25mm…

[0388] 25mm<Warp Amount…×

[0389] (Evaluation of heat resistance: Measurement of film glass transition temperature)

[0390] The epoxy resin composition was cured by the method described in the above (Evaluation of Warpage) to obtain a cured product, and then the aluminum foil was peeled off to take out the cured product layer.

[0391] The cured product layer was subjected to DMA measurement (RSA-G2, manufactured by TA Instruments, Inc.) at a temperature increase rate of 4° C. / min from 25° C. to 250° C., and the temperature at which tan δ showed a maximum value was defined as the glass transition temperature.

[0392] When the glass transition temperature of the thin film is 160° C. or higher, the heat resistance is considered to be good.

[0393] (Strength evaluation: Measurement of film tensile strength)

[0394] The epoxy resin composition was cured by the method described in the above (Evaluation of Warpage) to obtain a cured product, and then the aluminum foil was peeled off to take out the cured product layer.

[0395] The cured product layer thus taken out was cut into pieces having a width of 5 mm and a length of 4 cm to obtain test pieces.

[0396] The cut test pieces were subjected to a tensile test (AUTOGRAPH AGS-X 5 kN, manufactured by Shimadzu Corporation) at a tensile speed of 100 mm / min in a constant temperature and humidity chamber at 23°C and 50% RH, and the tensile strength was calculated from the breaking point.

[0397] 〔Ingredients record〕

[0398] Hereinafter, each component in the following Table 1 to Table 3 is shown as the components used in the epoxy resin compositions of Examples and Comparative Examples.

[0399] (Component (A): epoxy resin)

[0400] A-1: EXA850CRP (BisA type liquid epoxy resin, epoxy equivalent 190 g / eq, manufactured by DIC Corporation)

[0401] A-2: EXA830CRP (BisF type liquid epoxy resin, epoxy equivalent 160 g / eq, manufactured by DIC Corporation)

[0402] A-3: HP4032D (naphthalene-based liquid epoxy resin, epoxy equivalent 142 g / eq, manufactured by DIC Corporation)

[0403] A-4: NC-3000 (biphenyl type solid epoxy resin, epoxy equivalent 275 g / eq, manufactured by Nippon Kayaku Co., Ltd.)

[0404] A-5: YX4000 (biphenyl type solid epoxy resin, epoxy equivalent 186 g / eq, manufactured by Mitsubishi Chemical Corporation)

[0405] A-6: HP-4710 (naphthalene-based tetrafunctional solid epoxy resin, epoxy equivalent 170 g / eq, manufactured by DIC Corporation)

[0406] (Component (B): specific curing agent)

[0407] B-1: HPC-8000-65T (a toluene solution of an active ester curing agent having a solid content of 65%, an active group equivalent of 223 g / eq, manufactured by DIC Corporation)

[0408] B-2: LA-3018-50P (a 1-methoxy-2-propanol solution containing a phenolic curing agent having a triazine skeleton and having a solid content of 50%, an OH group equivalent of 151 g / eq, manufactured by DIC Corporation)

[0409] B-3: CYTESTER (registered trademark) TA (bisphenol A type cyanate ester curing agent, active group equivalent 139 g / eq, manufactured by Mitsubishi Gas Chemical Co., Ltd.)

[0410] (Component (C): Compounds represented by the general formula (1) and the general formula (2))

[0411] ·C-1: 2-(2-Hydroxyphenyl)imidazole (manufactured by Ambeed, Inc.)

[0412] ·C-2: 2-(2-Hydroxyphenyl)benzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0413] ·C-3: 2-(2-Hydroxyphenyl-5-methoxyphenyl)benzimidazole (manufactured by AOB ChemUSA)

[0414] C-4: 2-(2-Hydroxyphenyl)benzimidazole-6-carboxylic acid (manufactured by Apollo Scientific Ltd.)

[0415] (Comparative compound not belonging to component (C))

[0416] · R-1: DMAP (4-dimethylaminopyridine, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0417] ·R-2: 1B2PZ (1-benzyl-2-phenylimidazole, manufactured by Shikoku Chemical Holdings Co., Ltd.)

[0418] ·R-3: 2P4MZ (2-phenyl-4-methylimidazole, manufactured by Shikoku Chemical Holdings Co., Ltd.)

[0419] ·R-4: 2MZ-A (2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, manufactured by Shikoku Chemical Holdings Co., Ltd.)

[0420] (Ingredient (D): filler)

[0421] D-1: SO-E2 (spherical silica filler, average particle size 0.5 μm, manufactured by ADMATECHS)

[0422] (Component (E): solvent)

[0423] ·E-1: Methyl ethyl ketone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0424] · E-2: Cyclohexanone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0425] (Component (F): other curing agent)

[0426] F-1: HF-1M (phenol novolac resin curing agent, OH group equivalent 106 g / eq, manufactured by UBE)

[0427] (Component (G): thermoplastic resin)

[0428] G-1: PKHB (phenoxy resin, weight average molecular weight 32,000, manufactured by Gabriel Phenoxies)

[0429] (Component (H): silane coupling agent)

[0430] ·H-1: KBM-573 (aminosilane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0431] [Examples 1 to 22], [Comparative Examples 1 to 7]

[0432] The respective components were blended in the ratios (parts by mass) shown in Tables 1 to 3, and epoxy resin compositions were prepared by the above-mentioned method.

[0433] The various properties of the prepared epoxy resin composition were measured and evaluated by the above-mentioned methods.

[0434] [Table 1]

[0435]

[0436] [Table 2]

[0437]

[0438] [Table 3]

[0439]

[0440] Comparison of Examples 1 to 6 using a phenolic curing agent containing a triazine skeleton as component (B) with Comparative Examples 1 to 2 shows that the inclusion of component (C) results in high varnish storage stability and low warpage, and the glass transition temperature is also increased by approximately 20 to 30° C., which is very excellent. In addition, with respect to tensile strength, comparison of Examples 1 and 2 with Comparative Example 1, and Examples 3 to 6 with Comparative Example 2, which have the same type of curing agent and compounding amount, shows that the Example group shows higher tensile strength.

[0441] Compared with Comparative Examples 3 to 5 of the same compounding system, Examples 7 to 15 using only an active ester curing agent or a phenolic curing agent containing a triazine skeleton as component (B) have a warpage of about 20 mm less, a glass transition temperature of about 10 to 30°C higher, and a maximum tensile strength of 28 MPa higher, and are particularly excellent in warpage, heat resistance, and strength. In addition, it can be seen that the storage stability of the varnish is also good.

[0442] If Examples 16 to 22 using a cyanate curing agent and a phenolic curing agent or an active ester curing agent containing a triazine skeleton as component (B) are compared with Comparative Examples 6 and 7, it can be seen that the glass transition temperature is above 160°C, which is not a problem in practical use, but the varnish storage stability of Comparative Examples 6 and 7 is very poor and impractical. On the other hand, it can be seen that by using component (C), the varnish storage stability can be drastically improved. In addition, if Examples 16 to 20 of the same compounding system are compared with Comparative Example 6, and Examples 21 and 22 are compared with Comparative Example 7, it can be seen that the Examples are superior in terms of warpage and film tensile strength.

[0443] As described above, it can be seen that in the Example group containing the component (C) in addition to the specific curing agent (B), the varnish storage stability, warpage, glass transition temperature, and tensile strength can be improved, and a special effect can be exerted.

[0444] This application is based on Japanese patent application (Japanese Patent Application No. 2023-109093) filed with the Japan Patent Office on July 3, 2023, the contents of which are incorporated herein by reference.

[0445] Industrial Applicability

[0446] The epoxy resin composition of the present embodiment has excellent stability and reactivity as well as low warpage, high heat resistance, and high strength. Therefore, it has industrial applicability in the field of film materials such as sealing materials for electrical and electronic components such as relay sealing materials, various insulating liquid adhesives, mold bonding pastes, conductive pastes, thermal conductive pastes and other paste materials, solder resist inks, hole filling inks and other ink materials, base resins for fiber-reinforced plastics, resin materials such as impregnation fixing materials for motor coils, interlayer insulating films, film-type solder resist layers, sealing sheets for semiconductor packages, mold bonding films, conductive films, anisotropic conductive films, non-conductive films, thermal conductive films and other film materials.

[0447] In particular, for multilayer printed circuit boards, coreless substrates, and large package substrates for high-speed servers and network servers, low warping, high heat resistance, and high strength are further required. Therefore, the film-type adhesive, printed circuit board, semiconductor chip package, and electronic device of the present invention can be effectively utilized.

Claims

1. An epoxy resin composition comprising: Component (A): epoxy resin; Component (B): at least one curing agent selected from the group consisting of a phenolic curing agent containing a triazine skeleton, an active ester curing agent, and a cyanate curing agent; and Component (C): a compound represented by the following formula (1) and / or a compound represented by the following formula (2), In formula (1) and (2), R1 and R2 are each independently any one selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent, R1 and R2 may be the same or different, and R1 and R2 may be bonded to form a non-aromatic condensed ring; 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; Y and Z 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 be substituted, an alkoxy group having 1 to 20 carbon atoms which may be substituted, an alkenyl group having 2 to 20 carbon atoms which may be substituted, an aryl group having 6 to 20 carbon atoms which may be substituted, an aryloxy group having 6 to 20 carbon atoms which may be substituted, and an acyl group having 1 to 20 carbon atoms which may be substituted, Y and Z may be the same or different, and two or more Ys and two or more Zs may be bonded to each other to form a monocyclic or condensed ring; m and n are integers of 1 to 4. 2 . The epoxy resin composition according to claim 1 , further comprising component (D): a filler.

3. The epoxy resin composition according to claim 1, wherein In the component (C), Y and Z are 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 with a hydroxyl group and / or a carboxyl group as a substituent, an alkoxy group having 1 to 20 carbon atoms with a hydroxyl group and / or a carboxyl group as a substituent, an aryl group having 6 to 20 carbon atoms with a hydroxyl group and / or a carboxyl group as a substituent, an aryloxy group having 6 to 20 carbon atoms with a hydroxyl group and / or a carboxyl group as a substituent, and an acyl group having 1 to 20 carbon atoms with a hydroxyl group and / or a carboxyl group as a substituent.

4. The epoxy resin composition according to claim 1, wherein In the component (C), The compound represented by the formula (1) is any one selected from the group consisting of 2-(2-hydroxyphenyl)imidazole, 2-(2-hydroxyphenyl)-4(5)-methylimidazole, 4-ethyl-(2-hydroxyphenyl)-5-methylimidazole, (2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxyphenyl)-5-methylimidazole and 2-(2-hydroxy-3(5)-methoxyphenyl)imidazole, and / or The compound represented by the formula (2) is 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. The epoxy resin composition according to claim 4 , further comprising component (D): a filler. 6 . A resin paste comprising the epoxy resin composition according to claim 1 . 7 . A film-type adhesive comprising a support, and a resin layer comprising the epoxy resin composition according to claim 1 on the support. 8 . A film-type adhesive comprising a support, a resin layer comprising the epoxy resin composition according to claim 1 on the support, and a protective layer on the resin layer. 9 . A printed wiring board comprising a cured product layer of the epoxy resin composition according to claim 1 . 10 . A semiconductor chip package comprising a cured product layer of the epoxy resin composition according to claim 1 .

11. An electronic device comprising the printed circuit board according to claim 9. 12 . An electronic device comprising the semiconductor chip package according to claim 10 .

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