Epoxy resin composition, adhesive film, printed wiring board, semiconductor chip package, semiconductor device, and application method of adhesive film

Abstract

To obtain an epoxy resin composition having excellent storage stability after formed into a film, being excellent in micro-wiring embedding property and curing performance, and having both storage stability and reactivity.SOLUTION: An epoxy resin composition contains an epoxy resin (A) and a latent curing agent (B) while the latent hardening agent (B) is a solid at 25°C.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an epoxy resin composition, an adhesive film, a printed wiring board, a semiconductor chip package, a semiconductor device, and a method of using the adhesive film. [Background technology]

[0002] Conventionally, thermosetting resin compositions containing epoxy resins and the like, which have excellent adhesive properties and high reliability, have been used as adhesives for semiconductor elements and printed wiring boards. The components of the thermosetting resin composition generally include an epoxy resin, a curing agent such as a phenolic resin that is reactive with the epoxy resin, and a curing catalyst that promotes the reaction between the epoxy resin and the curing agent. In recent years, the performance of semiconductor elements and printed wiring boards has improved, and build-up layers are used and the wiring is multi-layered, which requires finer wiring, higher density, and lower dielectric loss tangent. In addition, with the multi-layer mounting of semiconductor elements and printed wiring boards, adhesives that can be cured under low temperature conditions are required.

[0003] In response to this, various efforts are being made. For example, Patent Document 1 discloses an epoxy resin composition for forming an insulating layer of a multilayer printed wiring board, which contains (A) an epoxy resin, (B) an active ester compound as a curing agent for the epoxy resin, (C) a triazine-containing cresol novolac resin, and (D) an inorganic filler having an average particle size of 1 μm or less, and the content of (D) the inorganic filler having an average particle size of 1 μm or less is 48% by mass or more and 85% by mass or less when the non-volatile components in the epoxy resin composition are taken as 100% by mass. Patent Document 1 discloses that the epoxy resin composition exhibits high adhesion to a plated conductor and can achieve a low linear expansion coefficient and a low dielectric loss tangent for the insulating layer.

[0004] In addition, Patent Document 2 discloses an epoxy resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler that has been surface-treated with a specific surface treatment agent, as a resin composition for printed wiring that exhibits good reflow behavior in the component mounting process even when the printed wiring board is thin. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6190092 [Patent Document 2] JP 2020-045501 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, the epoxy resin compositions disclosed in Patent Documents 1 and 2 have problems in that the storage stability after film formation is insufficient, the embedding properties of microwiring are poor, and the curing performance is insufficient for practical use, resulting in poor warping of the substrate due to the need for high temperatures during curing. These properties leave room for improvement.

[0007] Therefore, an object of the present invention is to provide an epoxy resin composition which has good storage stability after being made into a film, good embedding properties for fine wiring and good resistance to warping of a substrate, and excellent curing performance, and to provide an adhesive film, a printed wiring board, a semiconductor chip package, a semiconductor device, and the like, which have a resin layer containing the epoxy resin composition. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors have conducted intensive research to solve the above-mentioned problems, and as a result have found that the above-mentioned problems can be solved by employing a latent curing agent (B) that satisfies specific conditions in a resin composition containing an epoxy resin (A) and a latent curing agent (B), and have thus completed the present invention. That is, the present invention is as follows.

[0009] [1] An epoxy resin (A); A latent hardener (B); Contains The epoxy resin composition, wherein the latent curing agent (B) is a solid at 25°C. [2] The epoxy resin composition according to [1] above, further comprising an alcohol (C) represented by the following formula (1):

[0010] [ka]

[0011] In the formula (1), R1 to R9 are each independently one selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkyl group, an aromatic group, a substituent containing a heteroatom, and a substituent containing a halogen atom. R1 to R9 may be the same or different. Any of R5 to R9 may be bonded to each other to form a ring structure. The ring structure may be a condensed ring with the benzene ring shown in the formula.

[0012] [3] The epoxy resin composition according to [1] or [2] above, wherein the latent curing agent (B) is an amine-based curing agent having an amine moiety. [4] The latent curing agent (B) is The particle size D50 at an undersize cumulative fraction of 50% is more than 0.3 μm and 10 μm or less, The epoxy resin composition according to any one of [1] to [3] above, wherein a particle size distribution represented by a ratio (D99 / D50) of a particle size D99 at an undersize cumulative fraction of 99% to a particle size D50 at an undersize cumulative fraction of 50% is 6 or less. [5] The latent curing agent (B) is Specific surface area value (= Y(m 2 / g) and the particle size D50 (=X (μm)) at an undersize cumulative fraction of 50% satisfy the relationship represented by the following formula (2). The epoxy resin composition according to any one of [1] to [4] above. 4.0X-1 ≦ Y ≦ 8.3X-1 (2) (When the latent curing agent (B) is a curing agent component encapsulated with an encapsulating agent, the curing agent component before encapsulation satisfies the above formula (2).) [6] The latent curing agent (B) is The composition has a core (c) which is a hardener component, and a shell (s) which covers the core (c), The shell (s) has at least a wave number of 1630 cm -1 over 1680cm -1 The following infrared absorbing bond (x) and the wave number 1680 cm -1 Over 1725cm -1 The following infrared absorbing bond (y) and wave number 1730cm -1 Over 1755cm -1 and a bonding group (z) that absorbs infrared light as follows: The epoxy resin composition according to any one of [1] to [5] above. [7] The epoxy resin composition according to any one of [2] to [6] above, wherein R1 in the formula (1) is a hydroxyl group. [8] The alcohol (C), For a total of 100 parts by mass of the epoxy resin (A) and the latent curing agent (B), Contains 0.001 parts by mass or more and 20 parts by mass or less, The epoxy resin composition according to any one of [2] to [7] above. [9] The alcohol (C), For a total of 100 parts by mass of the epoxy resin (A) and the latent curing agent (B), Contains 0.1 parts by mass or more and 20 parts by mass or less, The epoxy resin composition according to any one of [2] to [8] above.

[10] The epoxy resin composition according to any one of the above [1] to [9], further comprising, in addition to the latent curing agent (B), one or more curing agents selected from the group consisting of a phenol-based curing agent, an active ester curing agent, an amine-based curing agent, an acid anhydride-based curing agent, and a thiol-based curing agent.

[11] The epoxy resin composition according to any one of [1] to

[10] above, further comprising a film-forming polymer (D).

[12] The epoxy resin composition according to any one of [1] to

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

[13] The epoxy resin composition according to any one of [1] to

[12] above, wherein the filler (E) is an inorganic filler.

[14] The epoxy resin composition according to any one of [1] to

[13] above, further comprising an additive (F).

[15] A support; A resin layer comprising the epoxy resin composition according to any one of [1] to

[14] on the support; having, Adhesive film.

[16] The adhesive film according to

[15] above, having a thickness of 20 μm or less.

[17] The adhesive film according to

[15] or

[16] above, which is an adhesive film for forming a build-up layer of a printed wiring board.

[18] The adhesive film according to

[15] or

[16] above, which is an adhesive film for an insulating layer of a semiconductor chip package.

[19] A printed wiring board comprising a layer obtained by curing the adhesive film according to

[15] or

[16] .

[20] A semiconductor chip package comprising a layer of the cured adhesive film according to

[15] or

[16] . 〔twenty one〕 A semiconductor device comprising the printed wiring board according to

[19] and / or the semiconductor chip package according to

[20] . 〔twenty two〕 A method for using the adhesive film according to

[15] or

[16] above, comprising laminating the adhesive film under a pressure of 40 MPa or less, and then heating the same under a temperature of 220° C. or less to produce a laminate or a semiconductor chip package. Effect of the Invention

[0013] According to the present invention, an epoxy resin composition can be obtained which has good storage stability after being made into a film, is excellent in embedding properties for microwiring and curing performance, and is capable of achieving both storage stability and reactivity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] Hereinafter, an embodiment of the present invention (hereinafter, simply referred to as "the present embodiment") will be described in detail. The present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment. In other words, the present invention can be modified in various ways without departing from the gist of the present invention. In this specification, when a numerical value or physical property value is enclosed before and after "~", the values ​​before and after the "~" are included.

[0015] [Epoxy resin composition] The epoxy resin composition of the present embodiment comprises: An epoxy resin (A); Contains a latent hardener (B), The latent curing agent (B) is a solid at 25°C. By having the above-mentioned constitution, an epoxy resin composition can be obtained which has good storage stability after being made into a film, excellent microwiring embedding properties and curing performance, and excellent storage stability and reactivity. In addition, by using the epoxy resin composition of the present embodiment, it is possible to improve the reliability in adhesive films, printed wiring boards, semiconductor chip packages, semiconductor devices, and the like, which require multi-layering, finer and higher density wiring, lower dielectric tangent, and the like.

[0016] (Epoxy resin (A)) The epoxy resin composition of the present embodiment contains an epoxy resin (A). The epoxy resin (A) is not particularly limited, and various known epoxy resins can be appropriately selected and used. The epoxy resin (A) may be used alone or in combination of two or more kinds.

[0017] Examples of the epoxy resin (A) include, but are not limited to, bifunctional epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD ​​type epoxy resins, bisphenol AF type epoxy resins, tetrabromobisphenol A type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, tetrafluorobiphenyl type epoxy resins, tetrabromobiphenyl type epoxy resins, diphenyl ether type epoxy resins, benzophenone type epoxy resins, phenylbenzoate type epoxy resins, diphenyl sulfide type epoxy resins, diphenyl sulfoxide type epoxy resins, diphenyl sulfone type epoxy resins, diphenyl disulfide type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, hydroquinone type epoxy resins, methylhydroquinone type epoxy resins, dibutylhydroquinone type epoxy resins, resorcin type epoxy resins, methylresorcin type epoxy resins, catechol type epoxy resins, and N,N-diglycidylaniline type epoxy resins.

[0018] Examples of the epoxy resin (A) include trifunctional epoxy resins such as N,N-diglycidylaminobenzene type epoxy resins, o-(N,N-diglycidylamino)toluene type epoxy resins, and triazine type epoxy resins; tetrafunctional epoxy resins such as tetraglycidyldiaminodiphenylmethane type epoxy resins and diaminobenzene type epoxy resins; and multifunctional epoxy resins such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type epoxy resins, dicyclopentadiene type epoxy resins, naphthol aralkyl type epoxy resins, and brominated phenol novolac type epoxy resins.

[0019] Further, examples of the epoxy resin (A) include diepoxy resins such as (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, and dicyclopentadiene type diglycidyl ether; and triepoxy resins such as trimethylolpropane triglycidyl ether and glycerin triglycidyl ether.

[0020] Furthermore, examples of the epoxy resin (A) include alicyclic epoxy resins such as vinyl(3,4-cyclohexene) dioxide and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane; 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-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane.

[0021] Furthermore, examples of the epoxy resin (A) include 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, trimethylol Propane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentadiene type diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, vinyl(3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane, Glycidylamine type epoxy resins such as tetraglycidylbis(aminomethyl)cyclohexane, 1,3-diglycidyl-5-methyl-5-ethylhydantoin type epoxy resins, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane type epoxy resins, phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether, styrene oxide, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenyl Various epoxy resins that can also be used as reactive diluents, such as phenol glycidyl ether, N-glycidyl phthalimide, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α-pinene oxide, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, and neodecanoic acid glycidyl ester, are examples of such epoxy resins.

[0022] In the epoxy resin composition of the present embodiment, a liquid epoxy resin and a solid epoxy resin can be used in combination as the epoxy resin (A). When liquid epoxy resin and solid epoxy resin are used in combination, the mass ratio thereof (liquid epoxy resin: solid epoxy resin) is not particularly limited, but is preferably in the range of 1:0.1 to 1:6. By setting the mass ratio of liquid epoxy resin and solid epoxy resin in the above range, (i) in an adhesive film having a support and a resin layer, in which the epoxy resin composition of the present embodiment is used in the resin layer, appropriate adhesion is obtained, (ii) when used in the form of the adhesive film, sufficient flexibility is obtained, improving handling, and (iii) a cured product having sufficient breaking strength can be obtained. 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 further preferably in the range of 1:0.6 to 1:4.

[0023] The content of the epoxy resin (A) in the epoxy resin composition of this embodiment can be appropriately set according to the desired performance of the epoxy resin of this embodiment, and is not particularly limited, but from the viewpoint of curability, it is preferably 2.5 mass% or more, more preferably 5 mass% or more, and even more preferably 10 mass% or more. Also, from the viewpoint of film-forming property, it is preferably 99 mass% or less, more preferably 95 mass% or less, and even more preferably 90 mass% or less.

[0024] (Latent hardener (B)) The epoxy resin composition of the present embodiment contains a latent curing agent (B). The latent hardener (B) is a solid at room temperature (25°C). The epoxy resin composition of the present embodiment contains the latent curing agent (B) which is solid at room temperature (25° C.), and thus the stability at room temperature is improved and the reactivity with the epoxy resin (A) is improved. In addition, when a curing agent other than the latent curing agent (B) is used in combination, it can act as a curing catalyst, which is preferable.

[0025] As the latent curing agent (B) which is solid at room temperature (25° C.), an amine-based curing agent having an amine moiety is preferred. An "amine moiety" is an organic derivative of ammonia and is a functional group that behaves as a base. By using an amine-based curing agent having an amine moiety as the latent curing agent (B), it is possible to obtain an effect that high reactivity can be obtained at a predetermined temperature.

[0026] The latent curing agent (B) is not limited to the following, but examples thereof include imidazoles, imidazole-based adducts, amine adducts, and encapsulated versions of these. Specific examples include Amicure PN-23J, PN-40J, and MY-24 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and Fujicure FXR-1020 and FXR-1030 (manufactured by Fuji Chemical Industry Co., Ltd.). The latent curing agent (B) may be used alone or in combination of two or more kinds.

[0027] Furthermore, from the viewpoint of obtaining a homogeneous cured product of the epoxy resin composition of this embodiment and from the viewpoint of preventing aggregation between particles of the latent curing agent (B) to ensure good physical properties of the cured product of the epoxy resin composition, the latent curing agent (B) is preferably composed of particles having a particle diameter D50 of more than 0.3 μm and less than 10 μm at an undersize cumulative fraction of 50%, more preferably 1 μm or more and 8 μm or less, and even more preferably 1.5 μm or more and 5 μm or less. When the particle diameter D50 of the latent curing agent (B) is 10 μm or less, a homogeneous cured product tends to be obtained in the epoxy resin composition, and when the particle diameter D50 is more than 0.3 μm, aggregation between the latent curing agents can be suppressed, curing unevenness does not occur, and the heat resistance of the cured product tends to be improved. Methods for making the particle diameter D50 of the latent curing agent (B) more than 0.3 μm and not more than 10 μm include a method of performing mechanical crushing and a method of performing particle growth in a solvent.

[0028] The particle size distribution of the latent curing agent (B), expressed as the ratio of the particle size D99 at an integrated undersieve fraction of 99% to the particle size D50 at an integrated undersieve fraction of 50% (hereinafter sometimes simply referred to as "D99 / D50"), is preferably 6.0 or less, more preferably 5.5 or less, and even more preferably 5.0 or less, from the viewpoint of preventing aggregation between particles. When D99 / D50 is 6.0 or less, the powder particles of the latent curing agent (B) contain fewer coarse particles, which tends to suppress the formation of aggregates and to suppress the deterioration of the physical properties of the cured product of the epoxy resin composition. The smaller the D99 / D50 value, the sharper the particle size distribution of the latent curing agent (B), and the easier it is to obtain a homogeneous cured product in the epoxy resin composition of this embodiment, and the more favorable the curing performance tends to be. In addition, since the value of D99 / D50 is 6.0 or less, the particle size distribution of the latent curing agent (B) is narrow and particles having a relatively large particle size are unlikely to exist. Therefore, when the epoxy resin composition of the present embodiment is made into a film, the film tends to have excellent permeability into a predetermined gap.

[0029] In addition, it is preferable that D99 / D50 is 1.2 or more. By making D99 / D50 1.2 or more, the formation of many gaps between the particles of the latent curing agent (B) tends to be suppressed. D99 / D50 is more preferably 1.5 or more, even more preferably 1.7 or more, and even more preferably 2.0 or more.

[0030] The D99 / D50 of the latent hardener (B) can be controlled to 6 or less by a classification operation such as removing coarse particles and fine particles.

[0031] The latent curing agent (B) may be a single-layer particle, but may also be a core-shell type curing agent particle having a core of the curing agent component and a shell that covers the core. The hardener particles (hardener component) for epoxy resin used as the core are referred to as "hardener particles for epoxy resin (H)", "hardener particles (H)", or "hardener (H)". The core-shell type curing agent particles as the latent curing agent (B) have a core (hereinafter also referred to as "core (c)") formed from the epoxy resin curing agent particles (H) or the like, and a shell (hereinafter also referred to as "shell (s)") that covers the core (c), and the shell (s) has a wavelength of 1630 cm -1 Over 1680cm -1 A bond that absorbs infrared rays at a wave number of 1680 cm (hereinafter referred to as "bonding group (x)") and -1 Over 1725cm -1 The following bond group (hereinafter referred to as "bond group (y)") absorbs infrared rays at a wave number of 1730 cm -1 Over 1755cm -1 It is preferable that the polymer has at least the following infrared absorbing bonding group (hereinafter also referred to as "bonding group (z)") on its surface. When configured in this manner, the aggregation ratio between particles of the latent curing agent (B) is reduced, and the epoxy resin composition of the present embodiment tends to be excellent in all of curability, storage stability, and gap permeability. As a method for obtaining the latent curing agent (B) having the above-mentioned core-shell type curing agent particles, in which the shell (s) has the above-mentioned predetermined bonding group (x), bonding group (y) and bonding group (z), there can be mentioned a method in which a predetermined encapsulating agent is selected and reacted with the core curing agent component.

[0032] In addition, the latent hardener (B) has a specific surface area value (= Y(m 2 It is preferable that the particle size D50 (=X (μm)) at an undersize cumulative fraction of 50% satisfies the relationship represented by the following formula (2): 4.0X-1 ≦ Y ≦ 8.3X-1 (2) In the following formula (2), X represents the particle diameter D50 (μm) of the latent hardener (B) at an undersize cumulative fraction of 50%, and Y represents the specific surface area (m 2 / g). As a method for making the specific surface area value and the particle diameter D50 satisfy the relationship of the above formula (2), for example, a method of modifying the surface of the latent curing agent (B) can be mentioned. Furthermore, when Y is 4.0X-1 or more, aggregation between particles of the latent curing agent (B) can be suppressed, and when Y is 8.3X-1 or less, the stability after mixing the latent curing agent (B) and the epoxy resin (A) can be improved. In addition, when the latent curing agent (B) is a core-shell type curing agent particle having a core of a curing agent component and a shell covering the core, for example, when the curing agent component is encapsulated with an encapsulating agent, it is sufficient that the curing agent component before encapsulation satisfies the above formula (2).

[0033] The content of the latent curing agent (B) in the epoxy resin composition of the present embodiment can be appropriately set according to the desired performance and is not particularly limited, but from the viewpoint of reactivity, it is preferably 0.2 mass% or more, more preferably 1.0 mass% or more, and even more preferably 2.0 mass% or more. Also, from the viewpoint of stability, it is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less.

[0034] (Alcohol (C)) The epoxy resin composition of the present embodiment preferably further contains an alcohol (C) represented by the following general formula (1). By containing the alcohol (C), the epoxy resin composition of the present embodiment tends to have improved reactivity while maintaining stability.

[0035] [ka]

[0036] In the formula (1), R1 to R9 are each independently one selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkyl group, an aromatic group, a substituent containing a heteroatom, and a substituent containing a halogen atom. R1 to R9 may be the same or different. Any of R5 to R9 may be bonded to each other to form a ring structure. The ring structure may be a condensed ring with the benzene ring shown in the formula.

[0037] The alcohol (C) represented by the formula (1) has excellent coordination properties with the above-mentioned latent curing agent (B) and compatibility with the epoxy resin (A) due to the presence of an aromatic ring, and has the function of improving the curability of the epoxy resin composition of the present embodiment.

[0038] When the latent curing agent (B) is an amine-based curing agent that is solid at 25°C, the alcohol (C) does not act on the latent curing agent (B) under room temperature conditions. However, when the temperature is above a certain level, the alcohol (C) improves its solubility in the epoxy resin (A), and the SP value, which is the solubility parameter, approaches that of the latent curing agent (B), which is an amine-based curing agent, and the alcohol (C) improves the curing property by making the latent curing agent (B) more soluble in the epoxy resin (A). Therefore, by adding the alcohol (C) in the presence of the latent curing agent (B), which is an amine-based curing agent that is solid at 25°C, the epoxy resin composition of this embodiment can achieve both room temperature stability and curing property when heated. This effect is more pronounced when the latent curing agent (B) is a capsule type.

[0039] From the viewpoint of enhancing the coordination ability to the latent curing agent (B) and further improving the curability of the epoxy resin composition of the present embodiment, it is preferable that R1 in formula (1) representing the alcohol (C) is a hydroxyl group.

[0040] Furthermore, from the viewpoint of not inhibiting the coordination of the hydroxyl group due to steric hindrance, it is preferable that R2, R3 and R4 in the above formula (1) are hydrogen atoms.

[0041] Examples of the alcohol (C) represented by the formula (1) include, but are not limited to, 3-phenoxy-1-propanol, 3-phenoxy-1,2-propanediol, 3-phenoxy-1,3-propanediol, mephenesin (3-(2-methylphenoxy)-1,2-propanediol), guaifenesin (3-(2-methoxyphenoxy)propane-1,2-diol), bisphenol A (3-hydroxypropyl) glycidyl ether, bisphenol A (2,3-dihydroxypropyl) glycidyl ether, and a compound represented by the following formula (1-1) (hereinafter also referred to as "compound 1").

[0042] [ka]

[0043] Examples of the alcohol (C) represented by the formula (1) include a compound having a 1-propanol structure produced by ring-opening of a terminal epoxy group of a bisphenol F epoxy resin, a compound having a 1,2-propanediyl structure produced by ring-opening of a terminal epoxy group of a bisphenol F epoxy resin (e.g., bisphenol F glycidyl 2,3-dihydroxypropyl ether), a compound having a 1-propanol structure produced by ring-opening of a terminal epoxy group of a naphthalene epoxy resin, a compound having a 1-propanol structure produced by ring-opening of a terminal epoxy group of a naphthalene epoxy resin, compounds having a 1,2-propanediyl structure formed by ring-opening of the terminal epoxy group of a phenol novolac type epoxy resin; compounds having a 1,2-propanediyl structure formed by ring-opening of the terminal epoxy group of a phenol novolac type epoxy resin; compounds having a 1,2-propanediyl structure formed by ring-opening of the terminal epoxy group of a cresol novolac type epoxy resin; and compounds having a 1,2-propanediyl structure formed by ring-opening of the terminal epoxy group of a cresol novolac type epoxy resin. In particular, from the viewpoints of having a high effect of lowering the thickening onset temperature of the epoxy resin composition of the present embodiment and having good compatibility with the epoxy resin (A) to obtain a uniform epoxy resin composition, 3-phenoxy-1-propanol, 3-phenoxy-1,2-propanediol, bisphenol A (3-hydroxypropyl) glycidyl ether, bisphenol A (2,3-dihydroxypropyl) glycidyl ether, and the compound 1 are preferred as the alcohol (C).

[0044] The content of the alcohol (C) in the epoxy resin composition of the present embodiment can be appropriately set depending on the desired performance and is not particularly limited. From the viewpoint of improving the reactivity, however, the content is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, even more preferably 0.01 part by mass or more, and still more preferably 0.1 part by mass or more, per 100 parts by mass in total of the epoxy resin (A) and the latent curing agent (B). From the viewpoints of stability and physical properties after curing, the amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

[0045] (Other hardener components) The epoxy resin composition of the present embodiment may contain, as a curing agent component other than the above-mentioned latent curing agent (B), one or more curing agents selected from the group consisting of phenol-based curing agents, active ester curing agents, amine-based curing agents, acid anhydride-based curing agents, and thiol-based curing agents.

[0046] <Phenol-based hardener> The phenol resin-based curing agent is not particularly limited as long as it can cure the epoxy resin (A). Examples of the curing agent include phenol novolac, bisphenol A novolac, cresol novolac, naphthol novolac, and triazine ring-containing phenol novolac. From the viewpoint of improving the dielectric loss tangent of the epoxy resin composition of the present embodiment, the phenol-based curing agent is preferably a triazine ring-containing phenol novolak, specifically, LA3018, LA3018-50P, EXB9808, EXB9829 (manufactured by DIC Corporation), etc.

[0047] <Active ester hardener> The active ester curing agent is not particularly limited as long as it functions as a curing agent for the epoxy resin (A) and has an active ester, but a compound having two or more active ester groups in one molecule is preferred. From the viewpoint of heat resistance of the epoxy resin composition of the present embodiment, the active ester curing agent 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 even more preferably an active ester compound obtained by reacting a carboxylic acid compound with one or more selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound. And, an aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is even more preferable. And, an aromatic compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group, and the aromatic compound having two or more active ester groups in one molecule is even more preferable. The active ester curing agent may be linear or branched. In addition, when the "compound having at least two or more carboxylic acids in one molecule" is a compound containing an aliphatic chain, the active ester curing agent obtained by using the "compound having at least two or more carboxylic acids in one molecule" has high compatibility with the epoxy resin (A). In addition, when the active ester curing agent is a compound having an aromatic ring, the heat resistance of the epoxy resin composition of the present embodiment can be increased.

[0048] Here, the carboxylic acid compound used to generate the active ester curing agent is not limited to the following, but examples thereof 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 the heat resistance of the epoxy resin composition of the present embodiment, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred.

[0049] The thiocarboxylic acid compound used to generate the active ester curing agent includes, but is not limited to, thioacetic acid, thiobenzoic acid, and the like.

[0050] Examples of the phenol compound or naphthol compound used to generate the active ester curing agent include, but are not limited to, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolak.Among these, from the viewpoints of the heat resistance of the cured product obtained from the epoxy resin composition of the present embodiment and the solubility of the active ester curing agent, 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, phloroglucin, benzenetriol, dicyclopentadienyldiphenol, and phenol novolak are preferred, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyldiphenol, and phenol novolak are preferred. Hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadienyl diphenol, and phenol novolak are more preferred, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolak are even more preferred, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolak are even more preferred, dicyclopentadienyl diphenol and phenol novolak are particularly preferred, and dicyclopentadienyl diphenol is even more preferred.

[0051] The thiol compound used to generate the active ester curing agent includes, but is not limited to, benzenedithiol, triazinedithiol, and the like.

[0052] The active ester curing agent may be an active ester compound disclosed in JP-A-2004-277460, or may be a commercially available active ester compound. Commercially available active ester compounds are not limited to the following, but are preferably, for example, those containing a dicyclopentadienyl diphenol structure, acetylated phenol novolac, and benzoylated phenol novolac, and more preferably, those containing a dicyclopentadienyl diphenol structure. Examples of those containing a dicyclopentadienyl diphenol structure include EXB9451, EXB9460, and EXB9460S (manufactured by DIC Corporation), DC808 (manufactured by Mitsubishi Chemical Corporation) as an acetylated phenol novolac, and YLH1026 (manufactured by Mitsubishi Chemical Corporation) as a benzoylated phenol novolac.

[0053] <Amine-based hardener> Examples of the amine-based curing agent include, but are not limited to, dicyandiamide derivatives such as dicyandiamide, dicyandiamide-aniline adduct, dicyandiamide-methylaniline adduct, dicyandiamide-diaminodiphenylmethane adduct, and dicyandiamide-diaminodiphenyl ether adduct; guanidine salts such as guanidine nitrate, guanidine carbonate, guanidine phosphate, guanidine sulfamate, and aminoguanidine bicarbonate; acetyl guanidine, diacetyl guanidine, proline; Examples of such amines include pionyl guanidine, dipropionyl guanidine, cyanoacetyl guanidine, guanidine succinate, diethylcyanoacetyl guanidine, dicyandiamine, N-oxymethyl-N'-cyanoguanidine, N,N'-dicarbethoxyguanidine, metaphenylenediamine, paraphenylenediamine, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl methane, and 4,4'-diaminodiphenyl ether. When the above-mentioned latent curing agent (B) is an amine-based curing agent having an amine moiety, it can be distinguished from these amine-based curing agents other than component (B) based on whether or not it has latency.

[0054] <Acid anhydride curing agent> Examples of acid anhydride curing agents 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.

[0055] <Thiol-based curing agent> The thiol-based curing agent may be any agent containing two or more thiol groups in one molecule, and is not limited to the following. Examples of the thiol-based curing agent include 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, 1,3,5-tris(3-mercaptobutyloxyethyl)-1, Examples of the mercaptothiol include 3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 4-butanedithiol, 1,6-hexaneedithiol, and 1,10-decanedithiol. From the viewpoint of the impact resistance of a cured product obtained from the epoxy resin composition of this embodiment, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol tetrakis(3-mercaptopropionate), and pentaerythritol tetrakis(3-mercaptobutyrate) are preferred, and from the viewpoint of the low-temperature curing property of the epoxy resin composition of this embodiment, pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) are more preferred.

[0056] The content of the curing agent components other than the latent curing agent (B) in the epoxy resin composition of the present embodiment can be appropriately set according to the desired performance and is not particularly limited, but from the viewpoint of reactivity, it is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and even more preferably 1.0 mass% or more. Also, from the viewpoint of stability, it is preferably 50 mass% or less, more preferably 45 mass% or less, and even more preferably 40 mass% or less.

[0057] (Film-forming polymer (D)) The epoxy resin composition of the present embodiment may contain a film-forming polymer (D). As the film-forming polymer (D), any polymer that has the function of preventing the occurrence of cracks or breaks and maintaining the film shape when formed into a film by casting or applying and drying to a certain thickness can be used. Examples of the film-forming polymer (D) include, but are not limited to, phenoxy resin, polyvinyl butyral resin, polyvinyl acetal resin, and elastomers having functional groups such as carboxyl groups, hydroxyl groups, vinyl groups, and amino groups. The film-forming polymer (D) may be used alone or in combination of two or more kinds. As the film-forming polymer (D), a phenoxy resin having excellent long-term connection reliability is preferable. Examples of the phenoxy resin include, but are not limited to, bisphenol A phenoxy resin, bisphenol F phenoxy resin, bisphenol A bisphenol F mixed phenoxy resin, bisphenol A biphenyl mixed phenoxy resin, bisphenol A bisphenol S mixed phenoxy resin, fluorene ring-containing phenoxy resin, and caprolactone-modified bisphenol A phenoxy resin.

[0058] The molecular weight of the film-forming polymer (D) is not particularly limited, but the number average molecular weight is preferably 9,000 to 23,000, more preferably 9,500 to 21,000, and even more preferably 10,000 to 20,000. The number average molecular weight is the number average molecular weight calculated in terms of polystyrene by gel permeation chromatography (hereinafter referred to as GPC), and is the average value calculated in the range of polystyrene-equivalent molecular weights of 728 or more. By making the number average molecular weight of the film-forming polymer (D) 9,000 or more, it is possible to prevent the film-forming polymer (D) from slipping through the crosslinked structure of the cured epoxy resin (A), and to prevent a decrease in the cohesive strength of the cured product of the epoxy resin composition of this embodiment. This is therefore preferable because it can prevent a decrease in the connection reliability between substrates in a printed wiring board and between a printed wiring board and a semiconductor package. On the other hand, when the number average molecular weight of the film-forming polymer (D) is 23,000 or less, an adhesive film using the epoxy resin composition of this embodiment as a material for the adhesive layer can maintain high adhesion to a specified substrate or adherend such as an IC chip, and can suppress the occurrence of localized curing defects during connection, making it difficult for corrosion of wiring and electrodes to occur, and thus obtaining high insulation reliability, which is preferable.

[0059] The content of the film-forming polymer (D) in the epoxy resin composition of this embodiment can be appropriately set according to the desired performance and is not particularly limited, but from the viewpoint of preventing cracking after forming the epoxy resin composition of this embodiment into a film, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. Also, from the viewpoint of handling of the varnish and ease of preparation of the film, it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. By setting the content of the film-forming polymer (D) within the above numerical range, an epoxy resin composition can be obtained which has good storage stability when made into a film and is excellent in embedding property and curing performance.

[0060] (Filler (E)) The epoxy resin composition of the present embodiment preferably further contains a filler (E). The filler (E) is not particularly limited, but examples thereof include inorganic fillers and inorganic fillers treated with a silane coupling agent from the viewpoints of thermal expansion coefficient and thermal conductivity, and organic fillers from the viewpoints of improving adhesive strength and crack resistance. The filler (E) may be used alone or in combination of two or more. The shape of the filler (E) is not particularly limited, and may be, for example, any of an irregular shape, a spherical shape, and a scaly shape.

[0061] By including an inorganic filler in the epoxy resin composition of the present embodiment, the thermal expansion coefficient can be adjusted, and the heat resistance and moisture resistance tend to be improved. Examples of inorganic fillers include, but are not limited to, silicates such as talc, calcined clay, uncalcined clay, mica, and glass; oxides such as titanium oxide, aluminum oxide (alumina), fused silica (fused spherical silica, fused crushed silica), synthetic silica, and crystalline silica; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates such as barium sulfate and calcium sulfate; sulfites such as calcium sulfite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; and nitrides such as aluminum nitride, boron nitride, and silicon nitride. Among these, from the viewpoint of improving the heat resistance, moisture resistance, and strength of the cured product obtained from the epoxy resin composition of this embodiment, fused silica, crystalline silica, and synthetic silica powder are preferred, and any of silicon oxide, aluminum oxide, and boron nitride is preferred. By using these, the thermal expansion coefficient of the cured product obtained from the epoxy resin composition of the present embodiment can be reduced, which is expected to improve the performance of thermal cycle tests.

[0062] When an inorganic filler is used as the filler (E), the content of the inorganic filler in the epoxy resin composition of the present embodiment can be appropriately set depending on the desired performance and is not particularly limited, but is preferably 10 mass % or more and 90 mass % or less, and more preferably 20 mass % or more and 85 mass % or less, based on the total amount of the epoxy resin composition. By setting the content of the inorganic filler to 10% by mass or more, an excellent low coefficient of thermal expansion tends to be realized, and by setting the content of the inorganic filler to 90% by mass or less, an increase in the elastic modulus tends to be further suppressed.

[0063] The inorganic filler is preferably surface-treated with a silane coupling agent. Although the performance of the silane coupling agent can be exhibited even when the silane coupling agent is contained in the epoxy resin composition of the present embodiment, by performing surface treatment of the inorganic filler with the silane coupling agent, there is a tendency that the viscosity of the epoxy resin composition of the present embodiment can be further reduced.

[0064] Examples of silane coupling agents include, but are not limited to, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, and 3-chloropropyltrimethoxysilane. Among these, from the viewpoint of adhesive strength after curing of the epoxy resin composition of the present embodiment, a silane coupling agent having a polymerizable functional group is preferred.

[0065] In the epoxy resin composition of the present embodiment, the organic filler functions as an impact modifier having stress relaxation properties. The epoxy resin composition of the present embodiment contains an organic filler, which further improves adhesion to various connecting members. Also, the occurrence and progression of cracks tends to be suppressed.

[0066] Examples of organic fillers include, but are not limited to, acrylic resin, silicone resin, butadiene rubber, polyester, polyurethane, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic rubber, polystyrene, NBR, SBR, silicone-modified resin, and organic fine particles of copolymers containing these as components. From the viewpoint of improving adhesion, preferred examples of the organic fine particles include alkyl (meth)acrylate-butadiene-styrene copolymers, alkyl (meth)acrylate-silicone copolymers, silicone-(meth)acrylic copolymers, complexes of silicone and (meth)acrylic acid, complexes of alkyl (meth)acrylate-butadiene-styrene and silicone, and complexes of alkyl (meth)acrylate and silicone.

[0067] As the organic filler, organic fine particles having a core-shell structure, in which the composition of the core layer is different from that of the shell layer, can also be used. Examples of core-shell type organic fine particles include, but are not limited to, particles having a silicone-acrylic rubber core to which an acrylic resin is grafted, and particles having an acrylic resin grafted to an acrylic copolymer. The inclusion of the core-shell type organic fine particles reduces the elastic modulus, which tends to reduce the stress generated in the fillet and suppress the occurrence of cracks. In addition, if cracks do occur, the contained core-shell type organic fine particles act as a stress relaxant and tend to suppress the progression of the cracks.

[0068] The core layer is preferably made of a material having excellent flexibility, and may be made of, but is not limited to, silicone elastomers, butadiene elastomers, styrene elastomers, acrylic elastomers, polyolefin elastomers, silicone / acrylic composite elastomers, etc. On the other hand, the material constituting the shell layer is preferably a material having excellent affinity to other components of the semiconductor resin encapsulant, particularly to the epoxy resin. The material constituting the shell layer is not limited to the following, but may be, for example, an acrylic resin, an epoxy resin, or the like. Among these, the acrylic resin is particularly preferred from the viewpoint of affinity to other components in the epoxy resin composition of the present embodiment, particularly affinity to the epoxy resin (A).

[0069] When an organic filler is used as the filler (E), the content of the organic filler in the epoxy resin composition of the present embodiment can be appropriately set depending on the desired performance and is not particularly limited, but is preferably 1 mass % or more and 20 mass % or less, more preferably 2 mass % or more and 18 mass % or less, and even more preferably 3 mass % or more and 16 mass % or less, relative to the total amount of the epoxy resin composition. By setting the organic filler content to 1% by mass or more, stress relaxation is achieved, and the effect of improving the adhesive strength of the epoxy resin composition of the present embodiment is obtained. By setting the organic filler content to 20% by mass or less, the effect of improving the heat reflow resistance of the epoxy resin composition of the present embodiment is obtained.

[0070] (Additive (F)) The epoxy resin composition of the present embodiment may further contain other additives (F) in addition to the above-mentioned alcohol (C), film-forming polymer (D), and filler (E). As the additive (F), from the viewpoint of adjusting the viscosity of the epoxy resin composition of the present embodiment, for example, a reactive diluent, a solvent, a thermoplastic polymer, a stabilizer, a liquid stress reducing agent, a flame retardant, a leveling agent, and the like can be used. The additives (F) may be used alone or in combination of two or more. The content of the additive (F) can be appropriately set according to the desired performance and is not particularly limited, but is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.001% by mass or more, based on the entire epoxy resin composition of this embodiment. The content of the additive (F) is preferably less than 20% by mass, more preferably less than 15% by mass, even more preferably less than 10% by mass, even more preferably less than 8% by mass, even more preferably less than 7% by mass, particularly preferably less than 6% by mass, even more preferably less than 5% by mass, even more preferably less than 3% by mass, and especially very preferably less than 2% by mass.

[0071] <Reactive diluent> The reactive diluent reduces the viscosity of the epoxy resin composition of the present embodiment, and can react with the latent curing agent (B) to become a part of the cured product. The reactive diluent may be a compound containing one or more glycidyl groups in its molecule, and may include, but is not limited to, butyl glycidyl ether, diglycidyl aniline, N,N'-glycidyl-o-toluidine, phenyl glycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. Further, the above-mentioned epoxy resins that can be used as reactive diluents can be mentioned. That is, examples of the reactive diluent include 2-ethylhexyl glycidyl ether, cyclohexane dimethanol diglycidyl ether, neopentyl 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, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentadiene type diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, vinyl(3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane, tetraglycidyl bis( Glycidylamine type epoxy resins such as 1,3-diglycidyl-5-methyl-5-ethylhydantoin type epoxy resins, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane type epoxy resins, phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol Also included are various epoxy resins such as nol glycidyl ether, N-glycidyl phthalimide, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α-pinene oxide, allyl glycidyl ether, 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyloxiranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, and neodecanoic acid glycidyl ester. In addition, various monoepoxy compounds and glycidyl ether compounds of polyhydric alcohols can also be used as reactive diluents, but these have only one functional group (epoxy group, glycidyl group) that contributes to the reaction with the latent curing agent (B) in one molecule, and cannot form three-dimensional crosslinks during curing, so the glass transition temperature (Tg) and toughness of the cured product of the epoxy resin composition of this embodiment tend not to be sufficient. Therefore, as reactive diluents, compounds containing two or more glycidyl groups in one molecule are preferable because they can form three-dimensional crosslinks during curing. This tends to suppress the decrease in glass transition temperature (Tg) and toughness during curing. The reactive diluents may be used alone or in combination of two or more.

[0072] The content of the reactive diluent in the epoxy resin composition of the present embodiment can be appropriately set according to the desired performance, and is not particularly limited, but is preferably 1.0 part by mass or more and 30 parts by mass or less relative to 100 parts by mass of the epoxy resin (A). By making the content of the reactive diluent 1.0 part by mass or more, the increase in the viscosity of the epoxy resin composition at room temperature is suppressed, and when the epoxy resin composition of the present embodiment is used as a film for embedding wiring, good embedding properties tend to be obtained. In addition, the epoxy resin composition of the present embodiment tends to suppress the decrease in glass transition temperature (Tg) and toughness during curing, and to suppress the occurrence and progression of fillet cracks. On the other hand, by controlling the content of the reactive diluent to 30 parts by mass or less per 100 parts by mass of the epoxy resin (A), a decrease in adhesion to an adherend is suppressed, and peeling during a moisture absorption reflow test tends to be suppressed. Furthermore, in order to suppress an increase in the viscosity of the epoxy resin composition that occurs when the filler (E) is highly filled, the content of the reactive diluent may be adjusted to be large.

[0073] <Solvent> Examples of the solvent include, but are not limited to, halogen-based solvents such as dichloromethane and chloroform; aromatic solvents such as benzene, toluene, xylene, and mesitylene; ketone solvents such as aliphatic ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic ketones such as acetophenone. Solvents such as ethyl acetate, dimethylformamide, methyl cellosolve, propylene glycol monomethyl ether, etc. may also be used in combination with the above solvents. Among these, it is preferable to use ethyl acetate as the ester from the viewpoints of the solubility and boiling point of the epoxy resin composition of the present embodiment. The solvent to be combined with ethyl acetate is preferably an aromatic solvent such as toluene having a boiling point of not more than 120° C. The solvent may be used alone or in combination of two or more.

[0074] <Thermoplastic polymer> The thermoplastic polymer is not limited to the following, but may be, for example, a polyamide resin, a polyimide, a polyester resin, a polyurethane resin, an acrylic resin, a vinyl carboxylate, and a polyether resin. Among these, an acrylic resin is preferred, and a vinyl carboxylate is more preferred. The thermoplastic polymer may be used alone or in combination of two or more. The acrylic resin is preferably an acrylic resin having a glass transition temperature (Tg) of 25° C. or less, more preferably one or more resins selected from the group consisting of hydroxyl group-containing acrylic resins, carboxyl group-containing acrylic resins, acid anhydride group-containing acrylic resins, epoxy group-containing acrylic resins, isocyanate group-containing acrylic resins, and urethane group-containing acrylic resins, and even more preferably a phenolic hydroxyl group-containing acrylic resin. Here, the term "acrylic resin" refers to a resin containing a (meth)acrylate structure, and in these resins, the (meth)acrylate structure may be contained in the main chain or in the side chain. The number average molecular weight (Mn) of the acrylic resin is preferably 10,000 or more and 1,000,000 or less, more preferably 30,000 or more and 900,000 or less. Here, the number average molecular weight (Mn) of the acrylic resin is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography). When the acrylic resin has a functional group, the functional group equivalent is preferably 1,000 or more and 50,000 or less, and more preferably 2,500 or more and 30,000 or less. The vinyl carboxylate may contain, as a monomer unit, a monomer copolymerizable with the vinyl carboxylate, such as an allyl carboxylate or an alkyl (meth)acrylate, specifically, allyl acetate, methyl (meth)acrylate, and ethyl (meth)acrylate.

[0075] <Stabilizer> As the stabilizer, a material that improves storage stability can be used, and examples thereof include, but are not limited to, boric acid and cyclic borate ester compounds. A cyclic borate ester compound is one in which boron is contained in a cyclic structure. A preferred cyclic borate ester compound is 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane). The stabilizer may be used alone or in combination of two or more kinds.

[0076] <Liquid low stress agent> Examples of liquid stress reducing agents include, but are not limited to, organic rubbers such as polyalkylene glycols and their amine-modified derivatives, polybutadiene, and acrylonitrile; silicone rubbers such as dimethylsiloxane; and silicone oils. The liquid stress reducing agent may be used alone or in combination of two or more kinds. The content of the liquid stress reducing agent is not particularly limited, but is preferably 5.0 parts by mass or more and 40 parts by mass or less, and more preferably 10 parts by mass or more and 20 parts by mass or less, relative to the mass (100 parts by mass) of the epoxy resin (A).

[0077] <Flame retardants> Examples of the flame retardant include, but are not limited to, bromine-based flame retardants, phosphorus-based flame retardants, and inorganic flame retardants. Examples of bromine-based flame retardants include, but are not limited to, tetrabromophenol. Examples of phosphorus-based flame retardants include, but are not limited to, 9,10-dihydro-9-oxa-10-phosphananthrene-10-oxide and its epoxy derivatives, triphenylphosphine and its derivatives, phosphate esters, condensed phosphate esters, and phosphazene compounds. Examples of the nitrogen-based flame retardant include, but are not limited to, guanidine-based flame retardants, triazine structure-containing phenols, melamine polyphosphate, and isocyanuric acid. Examples of inorganic flame retardant compounds include, but are not limited to, magnesium hydroxide, aluminum hydroxide, etc. Of the inorganic flame retardant compounds, magnesium hydroxide is preferred from the viewpoint of heat resistance. The flame retardants may be used alone or in combination of two or more. 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, relative to the mass (100 parts by mass) of the epoxy resin (A).

[0078] <Leveling agent> The leveling agent is not limited to the following, but examples thereof include silicone-based leveling agents and acrylic-based leveling agents. The leveling agents may be used alone or in combination of two or more kinds.

[0079] [Adhesive film] The adhesive film of the present embodiment has a support and a resin layer containing the epoxy resin composition of the present embodiment on the support. The support is not limited to the following, but examples thereof include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, and polyimide, as well as release paper and metal foils such as copper foil and aluminum foil, which may be subjected to a matte treatment, corona treatment, or release treatment. The thickness of the support is preferably 10 μm or more and 150 μm or less. From the viewpoint of reliability, the resin layer preferably contains 50% by mass or more and 100% by mass or less of the epoxy resin composition of the present embodiment. The resin layer may further contain conductive particles. The adhesive film of this embodiment can be used as an adhesive film for forming a build-up layer of a printed wiring board, or as an adhesive film for an insulating layer of a semiconductor chip package. The printed wiring board of the present embodiment includes a cured product of the adhesive film, and the semiconductor chip package of the present embodiment includes a cured product of the adhesive film. The semiconductor device of the present embodiment includes the printed wiring board and / or the semiconductor chip package.

[0080] [Method for producing epoxy resin composition] The epoxy resin composition of the present embodiment can be produced by mixing the above-mentioned epoxy resin (A), the latent curing agent (B), and, if necessary, other curing agents other than the latent curing agent (B), the alcohol (C), the film-forming polymer (D), the filler (E), the additive (F), and the like. The mixing method can be a method known in the art. For example, the mixture can be heated to a temperature at which it does not harden, and mixed, or each resin composition can be dissolved or dispersed in an organic solvent to form a varnish.

[0081] [Method of producing adhesive film] In a method for producing an adhesive film, for example, an epoxy resin (A), a latent curing agent (B), and, if necessary, a curing agent other than the latent curing agent, an alcohol (C), a film-forming polymer (D), a filler (E), and an additive (F) are dissolved or uniformly dispersed in a solvent by heating, and then, if necessary, cooled to 50° C. or lower to obtain a varnish of an epoxy resin composition. The solid content concentration in the varnish is not particularly limited, but is preferably 30% by mass or more and 80% by mass or less.

[0082] Examples of the solvent include, but are not limited to, halogen-based solvents such as dichloromethane and chloroform; aromatic solvents such as benzene, toluene, xylene, and mesitylene; ketone solvents such as aliphatic ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic ketones such as acetophenone. In addition, other solvents such as ethyl acetate, dimethylformamide, methyl cellosolve, and propylene glycol monomethyl ether can also be used in combination. Among these, from the viewpoint of the solubility and boiling point of the epoxy resin composition, it is preferable to use ethyl acetate in combination as the other solvent. As the above-mentioned solvent to be combined with ethyl acetate, it is preferable to use an aromatic solvent having a boiling point of 120° C. or less, such as toluene. The solvent may be used alone or in combination of two or more.

[0083] In the manufacturing process of the adhesive film of this embodiment, it is preferable to dissolve the epoxy resin composition of this embodiment in a mixed solvent containing ethyl acetate at room temperature. Dissolving at room temperature here means that a solution state is obtained at room temperature when mixed at a solid content concentration of 10 mass%, and refers to a state in which the substantial absence of solid content is maintained for one day or more, preferably 30 days or more.

[0084] The adhesive film of this embodiment can be produced by applying the varnish of the above-mentioned epoxy resin composition onto a support film, and then heating and drying to remove the solvent and form a film. This results in a semi-cured adhesive film. As described above, the thickness of the adhesive film after heating and drying is preferably 5 μm or more and 200 μm or less, more preferably 5 μm or more and 120 μm or less, even more preferably 7 μm or more and 70 μm or less, and even more preferably 10 μm or more and 20 μm or less. From the viewpoint of reducing the amount of materials used, the adhesive film of this embodiment preferably has a thickness of 200 μm or less. More preferably, it is 120 μm or less, even more preferably, it is 70 μm or less, and even more preferably, it is 20 μm or less. Moreover, from the viewpoint of ensuring embeddability and insulation, the thickness is preferably 5 μm or more. More preferably, it is 7 μm or more, and even more preferably, it is 10 μm or more.

[0085] The heating and drying conditions are as follows: heating temperature is 60° C. to 150° C., preferably 90° C. to 120° C., and heating time is 1 minute to 20 minutes, preferably 2 minutes to 10 minutes. When the heating and drying conditions are within this range, the solvent remaining in the obtained adhesive film is sufficiently removed, and the volatile content in the adhesive film can be reduced to 1 mass % or less. In addition, the hardening of the adhesive film due to film formation can be suppressed, and when the adhesive film of this embodiment is used by laminating it on a predetermined inner layer circuit board, the embedding property between wirings can be ensured.

[0086] In the manufacturing process of the adhesive film, the method of applying the varnish containing the epoxy resin composition of the present embodiment to the support can be a known method, and includes, but is not limited to, a bar coater, a lip coater, a die coater, a roll coater, a doctor blade coater, and the like.

[0087] [Printed Wiring Board] The printed wiring board of this embodiment includes a layer obtained by curing the adhesive film of this embodiment. When a printed wiring board is manufactured using the adhesive film, the adhesive film manufactured by the above method is attached to a patterned inner layer circuit board, and laminated while applying pressure and heat from the support side. The inner layer circuit surface may be roughened in advance. Lamination is performed under normal pressure or reduced pressure in a batch system or a continuous system with a roll, and it is preferable to laminate both sides simultaneously. The lamination conditions at this time are preferably a pressure bonding temperature of 70°C to 150°C and a pressure bonding pressure in the range of 0.1 to 60 MPa. In addition, from the viewpoint of reducing voids, it is preferable to laminate under reduced pressure of 2 KPa or less. From the viewpoint of maintaining the thickness of the adhesive film after pressure bonding, the pressure bonding pressure is preferably 40 MPa or less. After lamination, the adhesive film is cooled to room temperature, the support is peeled off from the adhesive film, and the resin layer laminated on the inner layer circuit board is then heat cured. The curing conditions are preferably a curing temperature of 130 to 250° C. and a curing time of 30 to 180 minutes. Next, the via holes are formed by a laser such as a carbon dioxide laser, and then roughening treatment is performed with an oxidizing agent such as permanganate, dichromate, or ozone to remove smears and improve adhesion with plating. Then, a conductor circuit is selectively formed on the resin layer of the border layer by electroless plating or electrolytic plating, and at the same time, a conductor layer is formed on the inner wall of the via hole to form an outer layer circuit. Then, annealing is performed at a temperature in the range of 150 to 250°C for a time in the range of 30 to 60 minutes to improve adhesion between the conductor layer and the resin layer. On the conductor circuit layer thus obtained, the adhesive film of this embodiment is further used to repeat the above manufacturing method, thereby forming a multi-stage build-up layer to manufacture a multilayer printed wiring board. The heat curing is preferably carried out under conditions of 220° C. or less from the viewpoint of volatilizing the organic compound and suppressing decomposition.

[0088] [Semiconductor chip packages, semiconductor devices] The semiconductor chip package of this embodiment includes the cured adhesive film. The semiconductor device of the present embodiment includes the printed wiring board and / or the semiconductor chip package.

[0089] [How to use the adhesive film] As described above in the [Printed Wiring Board] section, the adhesive film of this embodiment is preferably laminated under a pressure of 40 MPa or less, and then heat-cured under heating conditions at a temperature of 220°C or less to produce a specified laminate or semiconductor chip package. The compression pressure is more preferably 20 MPa or less, and further preferably 10 MPa or less. The heat curing temperature is more preferably 200° C. or lower, and further preferably 180° C. or lower. By setting the compression pressure to 40 MPa or less, a thickness sufficient for practical use can be ensured after compression bonding. Furthermore, by setting the heat curing temperature to 220° C. or less, the organic compounds can be sufficiently volatilized, and further, decomposition of the resin layer of the adhesive film can be prevented. EXAMPLES

[0090] The present embodiment will be described in more detail below with reference to examples and comparative examples, but these are merely illustrative and the present invention is not limited to the following examples and comparative examples. In other words, a person skilled in the art can carry out the present invention by making various modifications to the examples shown below. In the following, unless otherwise specified, "parts" are based on mass. In addition, the values ​​of various manufacturing conditions and evaluation results in the following examples have the meaning of the upper or lower limit preferred values ​​in the embodiment of the present invention. The preferred range has the meaning of the above-mentioned upper or lower limit preferred value, and the preferred range may be a range defined by a combination of the above-mentioned upper or lower limit value and the values ​​of the following examples or values ​​between the examples.

[0091] [Production of constituent materials of epoxy resin composition] Hereinafter, examples of the production of the constituent materials used in the epoxy resin compositions of the Examples and Comparative Examples described later will be described. ((Production Example 1) Production of epoxy resin curing agent 1) One equivalent of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation: product name "jER828EL") and one equivalent of 2-ethyl-4-methylimidazole (converted into active hydrogen) were reacted at 80°C in a 1:1 mixed solvent of n-butanol and toluene. After that, the excess amine was distilled off together with the solvent under reduced pressure to obtain a block-shaped epoxy resin curing agent that was solid at 25°C. Next, the block-shaped epoxy resin curing agent was pulverized in a jet mill and further classified by a classifier to obtain a specific surface area of ​​3.63 m 2 Epoxy resin curing agent 1 was obtained, which is an epoxy resin curing agent having a distribution of 0.1 g / g, an undersieve average particle size D50 of 2.50 μm, and a D99 / D50 of 5.4.

[0092] ((Production Example 2) Production of Encapsulated Epoxy Resin Curing Agent 2) 100 parts by mass of the epoxy resin curing agent 1 was uniformly dispersed in 200 parts by mass of hexane, and 30 parts by mass of an encapsulating agent (manufactured by Tosoh Corporation: product name "MR-400") was added thereto. The mixture was reacted for 3 hours with stirring at 50°C to obtain an encapsulated epoxy resin curing agent 2 which was solid at 25°C. The obtained epoxy resin curing agent 2 was subjected to IR measurement, and the shell showed a wave number of 1630 cm -1 Over 1680cm -1 Bond group (x) that absorbs infrared light at the following wavelengths: 1680 cm -1 Over 1725cm -1 Bond group (y) that absorbs infrared light at the following wavelengths: 1730 cm -1 Over 1755cm -1 The following infrared absorbing peaks due to the bonding group (z) were confirmed.

[0093] ((Production Example 3) Production of epoxy resin curing agent 3) Using the epoxy resin curing agent 1 obtained in the above (Production Example 1), a Krypton Orb manufactured by EarthTechnica Corporation was used, and the temperature was 10°C, the humidity was 30%, the rotation speed was 13,500 rpm, the supply speed was 10 kg / hr, and the air volume was 3 m 3 / min, shape correction was performed. A cyclone collector and a bag filter were attached to the classifier, and classification was performed, resulting in a specific surface area of ​​2.67 m 2 Epoxy resin curing agent 3 having a particle size distribution of 1.0 μm / g, D50 of 3.1 μm, and D99 / D50 of 4.5 was obtained.

[0094] ((Production Example 4) Production of Encapsulated Epoxy Resin Curing Agent 4) 100 parts by mass of the epoxy resin curing agent 3 was uniformly dispersed in 200 parts by mass of hexane, and 20 parts by mass of an encapsulating agent (manufactured by Tosoh Corporation: product name "Coronate T100") was added. The mixture was allowed to react for 3 hours with stirring at 50°C, yielding an encapsulated epoxy resin curing agent 4 that was solid at 25°C. The obtained epoxy resin curing agent 4 was subjected to IR measurement, and the shell showed a wave number of 1630 cm -1 Over 1680cm -1 Bond group (x) that absorbs infrared light at the following wavelengths: 1680 cm -1 Over 1725cm -1 Bond group (y) that absorbs infrared light at the following wavelengths: 1730 cm -1 Over 1755cm -1 The following infrared absorbing peaks due to the bonding group (z) were confirmed.

[0095] ((Production Example 5) Production of Epoxy Resin Curing Agent 5) One equivalent of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation: product name "jER828EL") and one equivalent of 2-methylimidazole (converted into active hydrogen) were reacted at 80°C in a 1:1 mixed solvent of n-butanol and toluene. Then, the excess imidazole and the solvent were distilled off together under reduced pressure to obtain a solid block-shaped epoxy resin curing agent at 25°C. The obtained epoxy resin curing agent was pulverized in a turbo mill to obtain a specific surface area of ​​0.36 m. 2 Epoxy resin curing agent 5 having a molecular weight of 1.001g / g, an undersieve average particle size D50 of 9.80 μm, and a D99 / D50 of 4.2 was obtained.

[0096] ((Production Example 6) Production of Film-Forming Polymer D-1) 170 parts by mass of biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation: product name "YX4000"), 110 parts by mass of biphenol, 30 parts by mass of xylene, and 0.05 parts by mass of triethylamine were mixed and reacted for 2 hours at 170°C with stirring under a nitrogen atmosphere. After the reaction was completed, the temperature was raised to 200°C over 3 hours while removing xylene from the system, and the reaction was continued for another 7 hours at 200°C to obtain a film-forming polymer D-1 having a number average molecular weight of 22,500.

[0097] ((Production Example 7) Production of Alcohol C-1) Bisphenol A diglycidyl ether (BADGE, Aldrich reagent, epoxy equivalent 172 g / eq): 50 parts by mass, methanol: 10 parts by mass, water: 1 part by mass, and trimethylammonium chloride: 0.005 parts by mass were mixed and reacted at 60°C for 2 hours with stirring under a nitrogen atmosphere. After the reaction was completed, methanol and remaining water were distilled off under reduced pressure at 140° C. to obtain alcohol C-1 having an alcoholic hydroxyl group equivalent of about 20,000 g / eq.

[0098] [Method of evaluating characteristics] The methods for evaluating the properties of the resin compositions in the examples and comparative examples described below will be described below. ((1) Evaluation of film storage stability) A 50% MEK (methyl ethyl ketone) solution of the epoxy resin composition of each of the examples and comparative examples was prepared as a varnish. Immediately after preparing the varnish, the varnish was applied to a PET film to a thickness of about 50 μm using a coater, and then dried in an oven at 100° C. for 5 minutes to obtain an adhesive film. The obtained adhesive film was subjected to FT-IR measurement, and the 926 cm -1 The peak (P1) and the phenyl group-derived peak at 1510 cm -1 The peak ratio F1 (P1 / P2) to the peak (P2) was calculated. Furthermore, after storing this adhesive film at 9°C for 30 days, FT-IR measurement was performed in the same manner, and the peak ratio F2 (P1 / P2) after storage was calculated. To compare F1 and F2, the peak ratio remaining amount of the epoxy group ((F2 / F1) x 100) was calculated. If the peak ratio remaining amount of the epoxy group was 90% or more and 99% or more, it was evaluated as "◎", if it was 70% or more and less than 90%, it was evaluated as "○", if it was 50% or more and less than 70%, it was evaluated as "△", and if it was less than 50%, it was evaluated as "×".

[0099] ((2) Evaluation of embeddability) An FR-5 substrate (17 cm x 34 cm, thickness 0.4 mm) was provided with wiring lines having a line / space of 10 μm / 10 μm and a wiring thickness of 7 μm, which had been depicted by a direct imaging process using a dry film resist. Using a roll-type laminator, the adhesive film prepared in (1) above was laminated onto one side of the substrate with the PET film still attached under conditions of a compression temperature of 90°C, a compression pressure of 0.3 to 0.5 MPa, and a lamination speed of 0.4 m / min. Gaps between the wirings where no resin was present were judged to be air bubbles, and the presence of air bubbles was visually checked. When no air bubbles were present, the sample was rated as "◯", and when bubbles were present, the sample was rated as "×".

[0100] ((3) Evaluation of warpage) After lamination in the above ((2) Embeddability) test, the PET film was peeled off from the adhesive film, and further pressure cured at 175°C for 45 minutes at 40 MPa to obtain a test specimen. After curing, the specimen was placed at room temperature in a downward convex state, and when one 17 cm side of the test specimen was pressed onto a desk, the height by which the other side rose above the desk was measured. In this case, the height from the desk was evaluated as follows: less than 1.0 cm was evaluated as "◎", 1.0 cm or more but less than 1.5 cm was evaluated as "○", 1.5 cm or more but less than 3 cm was evaluated as "△", and 3 cm or more was evaluated as "×".

[0101] ((4) Evaluation of heat resistance) Of the test pieces prepared in the above ((3) Warpage), a portion containing no air bubbles was cut into a piece measuring 0.5 cm x 0.5 cm. The cut piece was heated at a constant temperature of 288°C using a measuring device TMAQ400 (manufactured by TA Instruments), and the time until a blister appeared was measured. Those that took 60 minutes or more for the swelling to occur were rated as "good", those that took 45 minutes or more but less than 60 minutes were rated as "good", and those that took 45 minutes or less were rated as "poor".

[0102] ((5) Evaluation of peel strength) The film-like adhesive from which the PET film was removed was sandwiched between an FR-5 substrate and a copper foil with a thickness of 1 / 2oz, and pressure-bonded at 165°C for 30 minutes at 40MPa. Next, a cut was made in the copper foil on the substrate at a width of 10mm and a length of 150mm, and the 90-degree peel strength was measured. Peel strength: 1.0 kgf / cm or more was rated as "◎", 0.8 to less than 1.0 kgf / cm was rated as "◯", 0.6 to less than 0.8 was rated as "△", 0.4 to less than 0.6 was rated as "×", and less than 0.4 was rated as "XX".

[0103] (6) Measurement of dielectric constant and dielectric loss tangent The PET films were peeled off, and 40 sheets of the film-like adhesive were stacked and cured under reduced pressure at 180° C. for 60 minutes to obtain a cured product. The resulting cured product was cut into a width of 2 mm and a length of 80 mm to obtain a test piece. The dielectric constant (ε) and dielectric loss tangent (tan δ) of this test piece were measured at a measurement frequency of 1.0 GHz by the cavity resonance method using a cavity resonator perturbation method dielectric constant measuring device manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technologies, Inc. Measurements were performed on five test pieces, and the average value was calculated. A value of √ε×tanδ less than 0.01 was evaluated as "◎", a value of 0.01 or more but less than 0.012 was evaluated as "◯", a value of 0.012 or more but less than 0.015 was evaluated as "△", and a value of 0.015 or more was evaluated as "×".

[0104] [Examples 1 to 10], [Comparative Examples 1 and 2] The components (A), (B), (D), other curing agent components, filler (E), and additive (F) were dissolved or uniformly dispersed in a solvent heated to 60°C in the blending ratios shown in Tables 1 and 2, and then cooled to 30°C. Component (C) was further mixed in and uniformly dispersed to obtain an epoxy resin composition. The epoxy resin composition was applied to a PET film to a thickness of about 50 μm using a die coater, and then dried in an oven at 100° C. for 5 minutes to prepare an adhesive film used in the above evaluation.

[0105] [Constituent materials of epoxy resin composition] The components listed in Tables 1 and 2 below are as follows. ((A) Epoxy resin) A-1: Epicron 850CRP (bisphenol A type epoxy resin, manufactured by DIC Corporation, epoxy equivalent 175g / eq) A-2: YX4000 (biphenyl type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 170g / eq) A-3: NC3000H (biphenyl aralkyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269g / eq) A-4: HP4710 (naphthalene type epoxy resin, manufactured by DIC Corporation, epoxy equivalent 170g / eq) A-5: YX7760 (fluorine-containing epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 235g / eq)

[0106] ((B) component) B-1: Epoxy resin curing agent 1 of Production Example 1 B-2: Epoxy resin curing agent 2 of Production Example 2 B-3: Epoxy resin curing agent 3 of Production Example 3 B-4: Epoxy resin curing agent 4 of Production Example 4 B-5: Epoxy resin curing agent 5 of Production Example 5

[0107] (Other hardener components) DMAP: 4-dimethylaminopyridine (manufactured by Koei Chemical Co., Ltd., moisture content 1.7%, specific surface area 0.1 m 2 / g, average particle size under sieve D50 is 15.4μm, D99 / D50 is 6.4) LA7054: (Phenol novolac resin, manufactured by DIC Corporation, hydroxyl equivalent: 125 g / eq) LA3018: (Phenol novolac resin, manufactured by DIC Corporation, hydroxyl equivalent: 150 g / eq) EXB9460S: (Activated ester resin, manufactured by DIC Corporation, ester equivalent: 223 g / eq) HPC8000: (Activated ester resin, manufactured by DIC Corporation, ester equivalent: 223 g / eq)

[0108] ((C) component) C-1: Alcohol of Production Example 7 C-2: 3-phenoxy-1-propanol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) C-3: 3-phenoxy-1,2-propanediol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0109] (D) Film-forming polymer D-1: Film-forming polymer of Production Example 6 D-2: YP50 (phenoxy resin (manufactured by Nippon Steel Chemical & Material Co., Ltd.))

[0110] ((E) component) E-1: Aminosilane-treated synthetic spherical silica SO-C2 (manufactured by Admatechs Co., Ltd.)

[0111] (Component (F)) F-1: YED216L (1,6-hexanediol diglycidyl ether, manufactured by Mitsubishi Chemical Corporation) F-2: CDMDG (1,4-cyclohexanedimethanol diglycidyl ether, Showa Denko K.K.)

[0112] [Table 1]

[0113] [Table 2]

[0114] As shown in Tables 1 and 2, in Examples 1 to 10, epoxy resin compositions were obtained that had good storage stability after being made into a film, were excellent in embedding properties for microwiring and curing performance, and were capable of achieving both storage stability and reactivity.

[0115] This application is based on a Japanese patent application (Patent Application No. 2020-212769) filed with the Japan Patent Office on December 22, 2020, and a Japanese patent application (Patent Application No. 2021-005649) filed with the Japan Patent Office on January 18, 2021, the contents of which are incorporated herein by reference. [Industrial Applicability]

[0116] The epoxy resin composition of the present invention has industrial applicability in the fields of adhesive films, printed wiring boards, semiconductor chip packages, semiconductor devices, and the like, in which multi-layering, finer and higher density wiring, lower dielectric tangent, and the like are required.

Claims

1. an epoxy resin (A); a latent curing agent (B); Contains The latent curing agent (B) is solid at 25°C, further containing an alcohol (C) represented by the following formula (1) (excluding bisphenol A (2,3-dihydroxypropyl) glycidyl ether, a compound represented by the following formula (1-1), bisphenol F glycidyl 2,3-dihydroxypropyl ether, bisphenol F bis(2,3-dihydroxypropyl) ether, bisphenol A bis(2,3-dihydroxypropyl) ether, a compound represented by the following formula (3), and a compound having a 1,2-propanediol structure produced by ring-opening of a terminal epoxy group of a naphthalene-type epoxy resin), Epoxy resin composition. 【Chemical 1】 (In the formula (1), R 1 to R 9 are each independently one selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkyl group, an aromatic group, a substituent containing a hetero atom, and a substituent containing a halogen atom; R 1 to R 9 may be the same or different; any of R 5 to R 9 may be bonded to each other to form a ring structure; and the ring structure may be a condensed ring with the benzene ring shown in the formula.) 【Chemistry 1-1】 【Chemistry 1-2】

2. The latent curing agent (B) is an amine-based curing agent having an amine moiety. The epoxy resin composition according to claim 1.

3. The latent curing agent (B) is The particle size D50 at an undersize cumulative fraction of 50% is more than 0.3 μm and 10 μm or less, a particle size distribution represented by the ratio (D99 / D50) of a particle size D99 at an undersieve cumulative fraction of 99% to a particle size D50 at an undersieve cumulative fraction of 50% is 6 or less; The epoxy resin composition according to claim 1 or 2.

4. The latent curing agent (B) is The composition has a core (c) which is a curing agent component, and a shell (s) which covers the core (c), The shell (s) has at least a wave number of 1630 cm -1 1680cm or more -1 The following infrared absorbing bonding group (x) and the wave number 1680 cm -1 1725cm or more -1 The following infrared absorbing bonding group (y) and the wave number 1730 cm -1 Over 1755cm -1 and a bonding group (z) that absorbs infrared light as follows: The epoxy resin composition according to any one of claims 1 to 3.

5. R in the formula (1) 1 is a hydroxyl group, The epoxy resin composition according to any one of claims 1 to 4.

6. The alcohol (C) With respect to a total of 100 parts by mass of the epoxy resin (A) and the latent curing agent (B), Contains 0.001 parts by mass or more and 20 parts by mass or less, The epoxy resin composition according to any one of claims 1 to 5.

7. The alcohol (C) With respect to a total of 100 parts by mass of the epoxy resin (A) and the latent curing agent (B), Contains 0.1 parts by mass or more and 20 parts by mass or less, The epoxy resin composition according to any one of claims 1 to 6.

8. In addition to the latent curing agent (B), the composition further contains one or more curing agents selected from the group consisting of phenol-based curing agents, active ester curing agents, amine-based curing agents, acid anhydride-based curing agents, and thiol-based curing agents. The epoxy resin composition according to any one of claims 1 to 7.

9. Further comprising a film-forming polymer (D), The epoxy resin composition according to any one of claims 1 to 8.

10. Further comprising a filler (E), The epoxy resin composition according to any one of claims 1 to 9.

11. The filler (E) is an inorganic filler. The epoxy resin composition according to claim 10.

12. Further comprising an additive (F), The epoxy resin composition according to any one of claims 1 to 11.

13. A support; a resin layer comprising the epoxy resin composition according to any one of claims 1 to 12 on the support; have, Adhesive film.

14. The thickness is 20 μm or less. The adhesive film according to claim 13.

15. An adhesive film for forming build-up layers on printed wiring boards. The adhesive film according to claim 13 or 14.

16. It is an adhesive film for the insulating layer of semiconductor chip packages. The adhesive film according to claim 13 or 14.

17. A printed wiring board comprising a layer of the cured adhesive film according to claim 13 or 14.

18. A semiconductor chip package comprising a layer of the cured adhesive film of claim 13 or 14.

19. A semiconductor device comprising the printed wiring board according to claim 17 and / or the semiconductor chip package according to claim 18.

20. The adhesive film according to claim 13 or 14 is laminated under a pressure of 40 MPa or less, and then heated at a temperature of 220°C or less to produce a laminate or a semiconductor chip package. How to use adhesive film.

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