Epoxy resin composition, adhesive film, printed wiring board, semiconductor chip package, semiconductor device, and method for using adhesive film

Abstract

An epoxy resin composition containing an epoxy resin (A) and a latent curing agent (B), wherein the latent curing agent (B) is solid at 25°C.

Description

Technology Field

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

[0002] Conventionally, as an adhesive for semiconductor devices or printed circuit boards, a thermosetting resin composition containing an epoxy resin, which exhibits excellent adhesion and high reliability, is used. As components of the thermosetting resin composition, 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 are generally used.

[0003] In recent years, as the performance of semiconductor devices and printed circuit boards has advanced, they utilize build-up layers and are multilayered; furthermore, there is a demand for miniaturization and high-density wiring, as well as low dielectric loss tangents. Additionally, with the multilayer packaging of semiconductor devices and printed circuit boards, there is a demand for adhesives capable of curing under low-temperature conditions.

[0004] In response to this, various measures are being taken.

[0005] For example, Patent Document 1 discloses an epoxy resin composition for forming an insulating layer of a multilayer printed circuit board, wherein the composition comprises (A) an epoxy resin, (B) an active ester compound as a curing agent for the epoxy resin, (C) a triazine-containing cresol novolak resin, and (D) an inorganic filler having an average particle size of 1 μm or less, wherein when the non-volatile component in the epoxy resin composition is 100 mass%, the content of (D) the inorganic filler having an average particle size of 1 μm or less is 48 mass% or more and 85 mass% or less. Patent Document 1 describes that the epoxy resin composition exhibits high adhesion to a plated conductor and can also achieve a low linear expansion rate and a low dielectric loss tangent of the insulating layer.

[0006] In addition, Patent Document 2 discloses an epoxy resin composition for printed circuits that exhibits good reflow behavior in a component mounting process even when the printed circuit board is thin, comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler surface-treated with a specific surface treatment agent. Prior art literature

[0007] Japanese Patent Publication No. 6190092 and Japanese Patent Publication No. 2020-045501 The problem to be solved

[0008] However, the epoxy resin compositions disclosed in Patent Documents 1 and 2 have problems such as insufficient storage stability after film formation, poor embedding of fine wiring, poor bendability of the substrate because high temperatures are required during curing, and insufficient curing performance for practical use, so there is room for improvement in these characteristics.

[0009] Therefore, the present invention aims to provide an epoxy resin composition having good preservation stability after film formation, good embedding ability of fine wiring and bendability of the substrate, and excellent curing performance, an adhesive film having a resin layer including the epoxy resin composition, a printed circuit board, a semiconductor chip package, and a semiconductor device. means of solving the problem

[0010] As a result of repeated careful consideration to solve the above-mentioned problem, the inventors discovered that the above-mentioned problem 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 thus completed the present invention.

[0011] That is, the present invention is as follows.

[0012] [1]

[0013] Epoxy resin (A) and

[0014] Potential curing agent (B)

[0015] Contains,

[0016] The above latent curing agent (B) is an epoxy resin composition that is solid at 25°C.

[0017] [2]

[0018] The epoxy resin composition described in [1] further comprising an alcohol (C) represented by the following formula (1).

[0019]

[0020] In the above formula (1), R1 to R9 are each independently selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkyl group, an aromatic group, a substituent including a heteroatom, and a substituent including a halogen atom. R1 to R9 may be the same or different, and any of R5 to R9 selected may be combined with each other to form a ring structure, and the ring structure may be a condensed ring with a benzene ring shown in the formula.

[0021] [3]

[0022] The epoxy resin composition described in [1] or [2], wherein the potential curing agent (B) is an amine-based curing agent having an amine group.

[0023] [4]

[0024] The above potential curing agent (B) is,

[0025] The particle size D50 of the cumulative load fraction of 50% exceeds 0.3㎛ and is 10㎛ or less, and

[0026] An epoxy resin composition described in any one of [1] to [3], wherein the particle size distribution, expressed as the ratio (D99 / D50) of particle size D99 with a total weight fraction of 99% and particle size D50 with a total weight fraction of 50%, is 6 or less.

[0027] [5]

[0028] The above potential curing agent (B) is,

[0029] Specific surface area value (=Y(m 2 / g)) and the particle size D50 (=X(㎛)) of the above body load cumulative fraction of 50% satisfy the relationship represented by the following formula (2),

[0030] An epoxy resin composition described in any one of [1] to [4] above.

[0031] 4.0X-1≤Y≤8.3X-1 (2)

[0032] (If the above potential curing agent (B) encapsulates the curing agent component with an encapsulating agent, the above curing agent component before encapsulation satisfies the above formula (2).)

[0033] [6]

[0034] The above potential curing agent (B) is,

[0035] It has a core (c) which is a curing agent component and a shell (s) that covers the core (c),

[0036] The above shell(s) is at least, wavenumber 1630 cm -1 Over 1680cm -1 A coupler (x) that absorbs infrared radiation below, and a wavenumber of 1680 cm -1 Over 1725cm -1 A coupler (y) that absorbs infrared radiation below, and a wavenumber of 1730 cm -1 Over 1755cm -1 having a coupler (z) that absorbs infrared rays as follows

[0037] An epoxy resin composition described in any one of [1] to [5] above.

[0038] [7]

[0039] An epoxy resin composition described in any one of [2] to [6], wherein R1 in the above formula (1) is a hydroxyl group.

[0040] [8]

[0041] The above alcohol (C),

[0042] For a total of 100 parts by mass of the above epoxy resin (A) and the above latent curing agent (B),

[0043] Containing 0.001 parts by mass or more and 20 parts by mass or less,

[0044] An epoxy resin composition described in any one of [2] to [7] above.

[0045] [9]

[0046] The above alcohol (C),

[0047] For a total of 100 parts by mass of the above epoxy resin (A) and the above latent curing agent (B),

[0048] Containing 0.1 parts by mass or more and 20 parts by mass or less,

[0049] An epoxy resin composition described in any one of [2] to [8] above.

[0050]

[10]

[0051] An epoxy resin composition described in any one of [1] to [9], further comprising, in addition to the above potential curing agent (B), one or more curing agents selected from the group consisting of phenolic curing agents, active ester curing agents, amine curing agents, acid anhydride curing agents and thiol curing agents.

[0052]

[11]

[0053] An epoxy resin composition described in any one of [1] to

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

[0054]

[12]

[0055] An epoxy resin composition described in any one of [1] to

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

[0056]

[13]

[0057] An epoxy resin composition described in any one of [1] to

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

[0058]

[14]

[0059] An epoxy resin composition described in any one of [1] to

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

[0060]

[15]

[0061] Support and,

[0062] A resin layer comprising an epoxy resin composition described in any one of [1] to

[14] on the above support

[0063] having

[0064] Adhesive film.

[0065]

[16]

[0066] An adhesive film described in

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

[0067]

[17]

[0068] The adhesive film described in

[15] or

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

[0069]

[18]

[0070] The adhesive film described in

[15] or

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

[0071]

[19]

[0072] A printed circuit board comprising a layer of adhesive film cured as described in

[15] or

[16] above.

[0073]

[20]

[0074] A semiconductor chip package comprising a cured layer of the adhesive film described in

[15] or

[16] above.

[0075]

[21]

[0076] A semiconductor device having a printed circuit board as described in

[19] above and / or a semiconductor chip package as described in

[20] above.

[0077]

[22]

[0078] A method of using an adhesive film, wherein the adhesive film described in

[15] or

[16] above is laminated under a compression pressure of 40 MPa or less, and then a laminate or semiconductor chip package is manufactured under a heating condition of a temperature of 220°C or less. Effects of the invention

[0079] According to the present invention, an epoxy resin composition is obtained that has good storage stability after film formation, excellent embedding and curing performance of fine wiring, and compatibility between storage stability and reactivity. Specific details for implementing the invention

[0080] Hereinafter, an embodiment for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail.

[0081] The present embodiment is an example for explaining the invention, and the invention is not limited to this embodiment. That is, various modifications are possible within the scope of the invention without departing from its essence.

[0082] Additionally, in this specification, when using "to" to express numerical or physical property values ​​placed before and after it, it is used to include the values ​​before and after it.

[0083] [Epoxy resin composition]

[0084] The epoxy resin composition of the present embodiment is,

[0085] Epoxy resin (A) and

[0086] Contains a latent curing agent (B),

[0087] The above potential curing agent (B) is solid at 25°C.

[0088] By having the above composition, an epoxy resin composition is obtained that has good storage stability after film formation, excellent fine wiring embedding and curing performance, and excellent storage stability and reactivity.

[0089] In addition, by using the epoxy resin composition of the present embodiment, reliability can be increased in adhesive films, printed circuit boards, semiconductor chip packages, and semiconductor devices that require multilayering, miniaturization and high density of wiring, and low dielectric loss tangent.

[0090] (Epoxy resin (A))

[0091] The epoxy resin composition of the present embodiment contains epoxy resin (A).

[0092] The epoxy resin (A) is not specifically limited and various known types can be appropriately selected and used.

[0093] The epoxy resin (A) may be used as a single type or in combination of two or more types.

[0094] As for the epoxy resin (A), examples include, but are not limited to: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD ​​type epoxy resin, bisphenol AF type epoxy resin, tetrabromobisphenol A type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, tetrafluorobiphenyl type epoxy resin, tetrabromobiphenyl type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenylbenzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy resin, methylhydroquinone type epoxy resin, dibutylhydroquinone type epoxy resin, resorcinol type epoxy resin, methylresorcinol type epoxy resin, catechol type epoxy resin, N,N-diglycidylaniline type epoxy resin, etc. Examples include difunctional epoxy resins.

[0095] In addition, as for the epoxy resin (A), examples include trifunctional epoxy resins such as N,N-diglycidylaminobenzene type epoxy resin, o-(N,N-diglycidylamino)toluene type epoxy resin, and triazine type epoxy resin; tetrafunctional epoxy resins such as tetraglycidyldiaminodiphenylmethane type epoxy resin and diaminobenzene type epoxy resin; polyfunctional epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene type epoxy resin, naphtholaralkyl type epoxy resin, and bromophenol novolak type epoxy resin.

[0096] In addition, as an epoxy resin (A), examples include diepoxy resins such as (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene 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.

[0097] In addition, as an epoxy resin (A), examples include alicyclic epoxy resins such as vinyl(3,4-cyclohexene)dioxide, 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 backbone such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane.

[0098] In addition, as the epoxy resin (A), for example, 2-ethylhexylglycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, hydrogenated bisphenol A type epoxy resin, silicone modified epoxy resin, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, 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)diooxide, Glycidylamine-type epoxy resins such as 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane and tetraglycidylbis(aminomethyl)cyclohexane, 1,3-diglycidyl-5-methyl-5-ethylhydantoin-type epoxy resin, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane-type epoxy resin, phenylglycidyl ether, cresylglycidyl ether, ps-butylphenylglycidyl ether, styrene oxide, p-tert-butylphenylglycidyl ether, o-phenylphenolglycidyl ether, p-phenylphenolglycidyl ether, N-glycidylphthalimide, n-butylglycidyl ether, 2-ethylhexylglycidyl ether, α-pinene oxide, allylglycidyl ether, Examples include various epoxy resins that can also be used as reactive diluents, such as 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyloxyranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, and neodecanoic acid glycidyl ester.

[0099] In the epoxy resin composition of the present embodiment, liquid epoxy resin and solid epoxy resin may be used in combination as the epoxy resin (A).

[0100] When liquid epoxy resin and solid epoxy resin are used together, their mass ratio (liquid epoxy resin:solid epoxy resin) is not particularly limited, but a range of 1:0.1 to 1:6 is preferred. By setting the mass ratio of liquid epoxy resin and solid epoxy resin to the above range, effects such as (i) obtaining suitable tackiness in an adhesive film having a support and a resin layer, and using the epoxy resin composition of the present embodiment in the resin layer, (ii) obtaining sufficient flexibility and improving handling when used in the form of the adhesive film, and (iii) obtaining a cured product having sufficient breaking strength are obtained.

[0101] In terms of the effects of (i) to (iii) above, 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 more preferably in the range of 1:0.6 to 1:4.

[0102] In the epoxy resin composition of the present embodiment, the content of the epoxy resin (A) can be appropriately set according to the desired performance of the epoxy resin of the present embodiment and is not particularly limited, but from the perspective of curability, it is preferably 2.5 mass% or more, more preferably 5 mass% or more, and even more preferably 10 mass% or more. In addition, from the perspective of film formation, it is preferably 99 mass% or less, more preferably 95 mass% or less, and even more preferably 90 mass% or less.

[0103] (Latent curing agent (B))

[0104] The epoxy resin composition of the present embodiment contains a latent curing agent (B).

[0105] The latent curing agent (B) is solid at room temperature (25℃).

[0106] The epoxy resin composition of the present embodiment includes a latent curing agent (B) that is solid at room temperature (25°C), thereby improving stability at room temperature and improving reactivity with the epoxy resin (A). Additionally, when other curing agents other than the latent curing agent (B) are used in combination, it is preferable because they can serve as curing catalysts.

[0107] As a latent curing agent (B) that is solid at room temperature (25℃), an amine-based curing agent having an amine group is preferred.

[0108] An "amine group" is an organic derivative of ammonia and is a functional group that behaves as a base.

[0109] By using an amine-based curing agent having an amine group as a potential curing agent (B), the effect of obtaining high reactivity at a predetermined temperature can be achieved.

[0110] Potential curing agents (B) are not limited to the following, but examples include imidazoles, imidazole-based adducts, amine adducts, and encapsulated forms thereof.

[0111] Specifically, examples include the Ajicure PN-23J, PN-40J, MY-24 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Fujicure FXR-1020, FXR-1030 (manufactured by Fuji Kasei Kogyo Co., Ltd.), etc.

[0112] The latent curing agent (B) may be used alone or in combination with two or more types.

[0113] In addition, the latent curing agent (B) is preferably composed of particles with a particle size D50 of 50% of the total weight that exceeds 0.3㎛ and is 10㎛ or less, in order to obtain a homogeneous cured product of the epoxy resin composition of the present embodiment and to prevent aggregation of particles of the latent curing agent (B) to ensure good physical properties of the cured product of the epoxy resin composition. More preferably, the particle size D50 is 1㎛ or more and 8㎛ or less, and even more preferably 1.5㎛ or more and 5㎛ or less. If the particle size D50 of the latent curing agent (B) is 10㎛ or less, there is a tendency to obtain a homogeneous cured product in the epoxy resin composition, and if the particle size D50 is greater than 0.3㎛, aggregation between latent curing agents can be suppressed, so uneven curing does not occur and the heat resistance of the cured product tends to improve.

[0114] Methods for making the particle size D50 of the latent curing agent (B) greater than 0.3 μm and less than or equal to 10 μm include mechanical grinding and particle growth in a solvent.

[0115] The latent curing agent (B) has a particle size distribution expressed as the ratio of particle size D99 with a 99% cumulative load fraction to particle size D50 with a 50% cumulative load fraction (hereinafter simply referred to as “D99 / D50”), which is preferably 6.0 or less for the purpose of preventing aggregation between particles, more preferably 5.5 or less, and even more preferably 5.0 or less.

[0116] Since D99 / D50 is 6.0 or less, there are fewer coarse particles among the powder particles of the latent curing agent (B), and the formation of aggregates is suppressed, which tends to suppress damage to the physical properties of the cured product of the epoxy resin composition.

[0117] The smaller the value of D99 / D50, the sharper the particle size distribution of the latent curing agent (B) is, and in the epoxy resin composition of the present embodiment, it is easier to obtain a homogeneous cured product, and good curing performance tends to be obtained.

[0118] 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 it is difficult for relatively large particles to exist. Therefore, when the epoxy resin composition of the present embodiment is formed into a film, the penetration into the predetermined gaps of the film tends to be excellent.

[0119] In addition, it is desirable that D99 / D50 be 1.2 or higher.

[0120] Since D99 / D50 is 1.2 or higher, it tends to suppress the formation of many gaps between the particles of the latent curing agent (B). D99 / D50 is more preferably 1.5 or higher, even more preferably 1.7 or higher, and even more preferably 2.0 or higher.

[0121] The D99 / D50 of the latent curing agent (B) can be controlled to 6 or less by classification operations such as the removal of coarse particles or fine particles.

[0122] In addition, 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 covering the core.

[0123] The curing agent particles for epoxy resin used as the core (curing agent component) are referred to as “curing agent particles for epoxy resin (H)”, “curing agent particles (H)”, or “curing agent (H)”.

[0124] The core-shell type curing agent particles as a latent curing agent (B) have a core (hereinafter also referred to as "core (c)") formed from curing agent particles (H) for epoxy resin, etc., and a shell (hereinafter also referred to as "shell (s)" covering the core (c), and the shell (s) has a wavenumber of 1630 cm-1 Over 1680cm -1 A coupler that absorbs infrared radiation (hereinafter also referred to as "coupler (x)") and a wavenumber of 1680 cm -1 Over 1725cm -1 A coupler that absorbs infrared radiation (hereinafter also referred to as "coupler (y)") and a wavenumber of 1730 cm -1 Over 1755cm -1 It is preferable to have a coupler that absorbs infrared rays (hereinafter also referred to as "coupler (z)") on at least its surface.

[0125] When configured in this way, the aggregation ratio of particles of the potential curing agent (B) is reduced, and the epoxy resin composition of the present embodiment tends to have excellent curability, storage stability, and interstitial penetration.

[0126] A method for obtaining a potential curing agent (B) in which the core-shell type curing agent particles as described above and the shell (s) have the aforementioned predetermined linkers (x), linkers (y), and linkers (z) can be a method of selecting a predetermined encapsulating agent and reacting them with the curing agent component of the core.

[0127] In addition, the latent curing agent (B) has a specific surface area value (=Y(m 2 It is desirable that the particle size D50 (=X(㎛)) of the above body weight accumulation fraction of 50% and the above body weight accumulation fraction satisfy the relationship expressed by the following formula (2).

[0128] 4.0X-1≤Y≤8.3X-1 (2)

[0129] In the following formula (2), X represents the particle size D50 (㎛) of the cumulative fraction of the latent curing agent (B) at 50%, and Y is the specific surface area value (m 2 / g) represents.

[0130] As a method to satisfy the relationship between the specific surface area value and the particle size D50 of the above equation (2), for example, a method of modifying the surface of the potential curing agent (B) can be used.

[0131] In addition, since Y is 4.0X-1 or higher, aggregation of particles of the latent curing agent (B) can be suppressed, and since Y is 8.3X-1 or lower, stability after mixing the latent curing agent (B) and the epoxy resin (A) can be improved.

[0132] In addition, if the potential 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, if the curing agent component is encapsulated by an encapsulating agent, the curing agent component before encapsulation satisfies the above formula (2).

[0133] In the epoxy resin composition of the present embodiment, the content of the latent curing agent (B) can be appropriately set according to desired performance and is not particularly limited, but from the perspective 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. In addition, from the perspective of stability, it is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less.

[0134] (Alcohol (C))

[0135] The epoxy resin composition of the present embodiment preferably further contains an alcohol (C) represented by the following general formula (1).

[0136] By containing alcohol (C), the epoxy resin composition of the present embodiment tends to have improved reactivity while maintaining stability.

[0137]

[0138] In the above formula (1), R1 to R9 are each independently selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkyl group, an aromatic group, a substituent including a heteroatom, and a substituent including a halogen atom. R1 to R9 may be the same or different, and any of R5 to R9 selected may be combined with each other to form a ring structure, and the ring structure may be a condensed ring with a benzene ring shown in the formula.

[0139] The alcohol (C) represented by the above formula (1) combines excellent coordination with the above-described potential curing agent (B) and compatibility with the epoxy resin (A) by having an aromatic ring, and has the function of improving the curability of the epoxy resin composition of the present embodiment.

[0140] 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, under conditions above a predetermined temperature, the solubility of the alcohol (C) in the epoxy resin (A) is improved, and the solubility parameter SP value approaches that of the latent curing agent (B), which is an amine-based curing agent. As a result, the curability is improved by the action of making the latent curing agent (B) easier to dissolve 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, it is possible to achieve both room temperature stability and curability upon heating in the epoxy resin composition of the present embodiment. This effect is more pronounced when the latent curing agent (B) is in the form of a capsule.

[0141] In addition, in order to increase coordination with the potential curing agent (B) and to further improve 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.

[0142] In addition, from the view that the coordination of the hydroxyl group is not hindered by steric hindrance, it is preferable that R2, R3, and R4 in the above formula (1) are hydrogen atoms.

[0143] The alcohol (C) represented by the above formula (1) is not limited to the following, but examples include 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”).

[0144]

[0145] In addition, the alcohol (C) represented by the above formula (1) may be, for example, a compound having a 1-propanol structure produced by ring-opening the terminal epoxy group of a bisphenol F-type epoxy resin, a compound having a 1,2-propanediol structure produced by ring-opening the terminal epoxy group of a bisphenol F-type epoxy resin (for example, bisphenol F glycidyl 2,3-dihydroxypropyl ether), a compound having a 1-propanol structure produced by ring-opening the terminal epoxy group of a naphthalene-type epoxy resin, a compound having a 1,2-propanediol structure produced by ring-opening the terminal epoxy group of a naphthalene-type epoxy resin, a compound having a 1-propanol structure produced by ring-opening the terminal epoxy group of a phenol novolak-type epoxy resin, a compound having a 1,2-propanediol structure produced by ring-opening the terminal epoxy group of a phenol novolak-type epoxy resin, a compound having a 1-propanol structure produced by ring-opening the terminal epoxy group of a cresol novolak-type epoxy resin, or a cresol novolak-type epoxy resin Examples include compounds having a 1,2-propanediol structure formed by ring opening of the terminal epoxy group.

[0146] In particular, in order to obtain a uniform epoxy resin composition because it has a high effect of lowering the thickening onset temperature of the epoxy resin composition of the present embodiment and has good compatibility with the epoxy resin (A), 3-phenoxy-1-propanol, 3-phenoxy-1,2-propanediol, bisphenol A(3-hydroxypropyl)glycidyl ether, bisphenol A(2,3-dihydroxypropyl)glycidyl ether, and the above compound 1 are preferred as the alcohol (C).

[0147] In the epoxy resin composition of the present embodiment, the content of alcohol (C) can be appropriately set according to desired performance and is not particularly limited, but from the view of improving reactivity, it is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, and even more preferably 0.1 parts by mass or more.

[0148] In addition, from the perspective of stability or physical properties after curing, 20 parts by mass or less is preferable, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

[0149] (Other curing agent components)

[0150] The epoxy resin composition of the present embodiment may include, as a curing agent component other than the latent curing agent (B) described above, one or more curing agents selected from the group consisting of phenolic curing agents, active ester curing agents, amine curing agents, acid anhydride curing agents, and thiol curing agents.

[0151] Phenolic Curing Agents

[0152] As for the phenol resin-based curing agent, it is not particularly limited as long as it can cure the epoxy resin (A), but examples include phenol novolak, bisphenol A novolak, cresol novolak, naphthol novolak, triazine ring-containing phenol novolak, etc.

[0153] In order to improve the dielectric loss tangent of the epoxy resin composition of the present embodiment, a phenol novolak containing a triazine ring is preferred as a phenolic curing agent. Specifically, examples include LA3018, LA3018-50P, EXB9808, EXB9829 (manufactured by DIC Co., Ltd.).

[0154] Active Ester Curing Agent

[0155] As an active ester curing agent, as long as it functions as a curing agent for epoxy resin (A) and has an active ester, it is not particularly limited, but a compound having two or more active ester groups in one molecule is preferred.

[0156] With regard to the 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 hydroxyl 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 compounds selected from the group consisting of phenolic compounds, naphthol compounds, and thiol compounds. Furthermore, an aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having phenolic hydroxyl groups is even more preferable. Furthermore, an aromatic compound obtained by reacting a compound having at least two carboxylic acids in one molecule with an aromatic compound having phenolic hydroxyl groups is even more preferable, and an aromatic compound having two or more active ester groups in one molecule of said aromatic compound is even more preferable.

[0157] The active ester curing agent may be in a straight chain or a branched form. In addition, if the “compound having at least two carboxylic acids in one molecule” is a compound containing an aliphatic chain, the active ester curing agent obtained using the “compound having at least two carboxylic acids in one molecule” has high compatibility with the epoxy resin (A). In addition, if such an 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.

[0158] Here, the carboxylic acid compounds used to produce the active ester curing agent are not limited to the following, but examples include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. In particular, from the perspective 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.

[0159] Thiocarboxylic acid compounds used to produce active ester curing agents are not limited to the following, but examples include thioacetic acid, thiobenzoic acid, etc.

[0160] Examples of phenol compounds or naphthol compounds used to produce active ester curing agents include, but are not limited to the following: hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolac, etc. Among these, in terms 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, phloroglucine, benzenetriol, dicyclopentadienyldiphenol, and phenol novolac are preferred, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolac are more preferred, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac are even more preferred, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol, and phenol novolac are even more preferred, dicyclopentadienyl diphenol and phenol novolac are particularly preferred, and dicyclopentadienyl diphenol is even more preferred.

[0161] Thiol compounds used to produce active ester curing agents are not limited to the following, but examples include benzenedithiol, triazinedithiol, etc.

[0162] As the active ester curing agent above, the active ester compound disclosed in Japanese Patent Publication No. 2004-277460 may be used, or a commercially available one may be used. The commercially available active ester compound is not limited to the following, but, for example, one containing a dicyclopentadienyl diphenol structure, an acetylated derivative of phenol novolac, or a benzoylated derivative of phenol novolac is preferred, and in particular, one containing a dicyclopentadienyl diphenol structure is more preferred. Examples of those containing a dicyclopentadienyl diphenol structure include EXB9451, EXB9460, EXB9460S (manufactured by DIC Corporation), DC808 (manufactured by Mitsubishi Chemical Corporation) as an acetylated derivative of phenol novolac, and YLH1026 (manufactured by Mitsubishi Chemical Corporation) as a benzoylated derivative of phenol novolac.

[0163] Amine-based curing agent

[0164] As amine-based curing agents, examples include, but are not limited to: dicyandiamide, dicyandiamide-aniline adduct, dicyandiamide-methylaniline adduct, dicyandiamide-diaminodiphenylmethane adduct, dicyandiamide-diaminodiphenyl ether adduct, etc.; guanidine salts such as guanidine nitrate, guanidine carbonate, guanidine phosphate, guanidine sulfamic acid, aminoguanidine bicarbonate, etc.; acetylguanidine, diacetylguanidine, propionylguanidine, dipropionylguanidine, cyanoacetylguanidine, guanidine succinate, diethylcyanoacetylguanidine, dicyandiamidine, N-oxymethyl-N'-cyanoguanidine, N,N'-dicarboethoxyguanidine, metaphenylenediamine, paraphenylenediamine, 3,3'-diaminodiphenylsulfone, Examples include 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, etc.

[0165] In addition, if the above-described potential curing agent (B) is an amine-based curing agent having an amine group, it can be distinguished from amine-based curing agents other than these (B) components by whether or not it has potential.

[0166] Acid anhydride-based hardening agent

[0167] Examples of acid anhydride-based curing agents include, but are not limited to the following: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.

[0168] Thiol-based curing agents

[0169] As a thiol-based curing agent, it is sufficient if it contains two or more thiol groups in one molecule, and is not limited to the following, but examples 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)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), Examples include dipentaerythritol hexakis(3-mercaptopropionate), 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluryl, 4-butanedithiol, 1,6-hexanedithil, 1,10-decandithil. In terms of impact resistance of the cured product obtained from the epoxy resin composition of the present 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 in terms of low-temperature curing properties of the epoxy resin composition of the present embodiment, pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) are more preferred.

[0170] In the epoxy resin composition of the present embodiment, the content of other curing agent components other than the potential curing agent (B) can be appropriately set according to the desired performance and is not particularly limited, but from the perspective 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. In addition, from the perspective of stability, it is preferably 50 mass% or less, more preferably 45 mass% or less, and even more preferably 40 mass% or less.

[0171] ( Film-forming polymer (D))

[0172] The epoxy resin composition of the present embodiment may contain a film-forming polymer (D).

[0173] As a film-forming polymer (D), any polymer having the function of preventing the occurrence of cracks or fissures and maintaining the film shape when formed into a film by casting or by applying and drying to a certain thickness can be used.

[0174] Film-forming polymers (D) are not limited to the following, but examples include phenoxy resin, polyvinyl butyral resin, polyvinyl acetal resin, and elastomers having functional groups such as carboxyl groups, hydroxyl groups, vinyl groups and amino groups.

[0175] The film-forming polymer (D) may be used as a single type or in combination of two or more types.

[0176] As the film-forming polymer (D), a phenoxy resin with excellent long-term connection reliability is preferred. Examples of phenoxy resins include, but are not limited to the following: bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A bisphenol F mixed type phenoxy resin, bisphenol A biphenyl mixed type phenoxy resin, bisphenol A bisphenol S mixed type phenoxy resin, fluorene ring-containing phenoxy resin, caprolactone-modified bisphenol A type phenoxy resin, etc.

[0177] The molecular weight of the film-forming polymer (D) is not particularly limited, but it is preferable that the number average molecular weight is 9,000 or more and 23,000 or less, more preferably 9,500 or more and 21,000 or less, and even more preferably 10,000 or more and 20,000 or less. Here, the number average molecular weight is the number average molecular weight in polystyrene equivalent by gel permeation chromatography (hereinafter referred to as GPC), and is a value calculated as an average value for the region where the polystyrene equivalent molecular weight is 728 or more.

[0178] Since the number average molecular weight of the film-forming polymer (D) is 9,000 or more, the film-forming polymer (D) can be suppressed from escaping from the cross-linked structure of the cured epoxy resin (A), thereby suppressing the decrease in the cohesive strength of the cured product of the epoxy resin composition of the present embodiment, and thus suppressing the decrease in the reliability of the connection between substrates within the printed circuit board or between the printed circuit board and the semiconductor package.

[0179] Meanwhile, since the number average molecular weight of the film-forming polymer (D) is 23,000 or less, the adhesive film using the epoxy resin composition of the present embodiment as the adhesive layer material can maintain high adhesion to a substrate or IC chip, and can also suppress the occurrence of localized curing defects during connection, so that corrosion of the wiring and electrodes is unlikely to occur and high insulation reliability is obtained, which is desirable.

[0180] In the epoxy resin composition of the present embodiment, the content of the film-forming polymer (D) can be appropriately set according to the desired performance and is not particularly limited, but from the perspective of preventing cracking after forming the epoxy resin composition of the present embodiment into a film, it is preferably 5 mass% or more, more preferably 10 mass% or more, and even more preferably 15 mass% or more. In addition, from the perspective of handling of the varnish or ease of manufacturing the film, it is preferably 90 mass% or less, more preferably 80 mass% or less, and even more preferably 70 mass% or less.

[0181] By setting the content of the film-forming polymer (D) to the above numerical range, an epoxy resin composition is obtained that has good storage stability when formed into a film and excellent embeddability and curing performance.

[0182] (Filling material (E))

[0183] The epoxy resin composition of the present embodiment preferably further includes a filler (E).

[0184] As for the filler (E), it is not particularly limited, but in terms of thermal expansion coefficient or thermal conductivity, inorganic fillers, inorganic fillers treated with a silane coupling agent, and in terms of improving adhesive strength and crack resistance, organic fillers, etc., may be used.

[0185] The filler (E) may be used as a single type or in combination with two or more types. In addition, the shape of the filler (E) is not particularly limited and may be any shape, such as irregular, spherical, or flake-like.

[0186] Since the epoxy resin composition of the present embodiment contains an inorganic filler, the coefficient of thermal expansion can be adjusted, and thus heat resistance and moisture resistance tend to be improved.

[0187] Examples of inorganic fillers include, but are not limited to, silicates such as talc, calcined clay, microclay, mica, and glass; oxides such as silica 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, fused silica, crystalline silica, and synthetic silica powder are preferred from the perspective of improving the heat resistance, moisture resistance, and strength of the cured product obtained from the epoxy resin composition of the present embodiment, and any one of silicon oxide, aluminum oxide, and boron nitride is also preferred. By using these, the coefficient of thermal expansion of the cured product obtained from the epoxy resin composition of the present embodiment can be suppressed, so improvements in cold-heat cycle tests are expected.

[0188] 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 according to desired performance and is not particularly limited, but is preferably 10 mass% or more and 90 mass% or less with respect to the total amount of the epoxy resin composition, and more preferably 20 mass% or more and 85 mass% or less.

[0189] By making the content of inorganic filler 10 mass% or more, there is a tendency to achieve an excellent low coefficient of thermal expansion. By making the content of inorganic filler 90 mass% or less, there is a tendency to further suppress the increase in elastic modulus.

[0190] It is preferable that the inorganic filler be surface-treated with a silane coupling agent.

[0191] Although the performance of the silane coupling agent is exhibited even when included in the epoxy resin composition of the present embodiment, there is a tendency to achieve even lower viscosity in the epoxy resin composition of the present embodiment by surface treatment of the inorganic filler with the silane coupling agent.

[0192] Examples of silane coupling agents include, but are not limited to the following: 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, 3-chloropropyltrimethoxysilane, etc.

[0193] Among these, a silane coupling agent having a polymerizable functional group is preferred in terms of the adhesive strength after curing of the epoxy resin composition of the present embodiment.

[0194] The organic filler functions as an impact dampener having stress-relaxing properties in the epoxy resin composition of the present embodiment.

[0195] The epoxy resin composition of the present embodiment contains an organic filler, thereby further improving adhesion to various connecting members. In addition, it tends to suppress the occurrence and progression of cracks.

[0196] Organic fillers may include, but are not limited to the following, examples of 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.

[0197] In terms of improving adhesion, the organic microparticles preferred are, for example, (meth)acrylate-butadiene-styrene copolymer, (meth)acrylate-silicon copolymer, silicon-(meth)acrylate copolymer, a complex of silicon and (meth)acrylic acid, a complex of (meth)acrylate-butadiene-styrene and silicon, and a complex of (meth)acrylate and silicon.

[0198] As the above organic filler, organic microparticles having a core-shell structure and having different compositions in the core layer and the shell layer may be used.

[0199] Examples of core-shell type organic microparticles include, but are not limited to, particles grafted with acrylic resin using a silicone-acrylic rubber core, and particles grafted with acrylic resin using an acrylic copolymer.

[0200] Due to the reduction in elastic modulus caused by the inclusion of core-shell type organic fine particles, stress generated in the fillet is reduced, which tends to suppress the occurrence of cracks. Furthermore, if a crack occurs, the included core-shell type organic fine particles act as a stress reliever, which tends to inhibit the propagation of the crack.

[0201] As the constituent material of the above core layer, it is preferable to use a material with excellent flexibility. The constituent material of the core layer is not limited to the following, but examples include silicone-based elastomers, butadiene-based elastomers, styrene-based elastomers, acrylic-based elastomers, polyolefin-based elastomers, and silicone / acrylic composite elastomers.

[0202] Meanwhile, as the constituent material of the shell layer, a material having excellent affinity for other components of the semiconductor resin sealant, particularly affinity for epoxy resin, is preferred. The constituent material of the shell layer is not limited to the following, but examples include acrylic resin and epoxy resin. Among these, acrylic resin is particularly preferred in terms of affinity for other components of the epoxy resin composition of the present embodiment, particularly affinity for epoxy resin (A).

[0203] 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 according to the desired performance and is not particularly limited, but is preferably 1 mass% or more and 20 mass% or less with respect to the total amount of the epoxy resin composition, more preferably 2 mass% or more and 18 mass% or less, and even more preferably 3 mass% or more and 16 mass% or less.

[0204] By having an organic filler content of 1 mass% or more, stress relief is applied, and the effect of improving the adhesion of the epoxy resin composition of the present embodiment is obtained. By having an organic filler content of 20 mass% or less, the effect of improving heat-resistant reflowability in the epoxy resin composition of the present embodiment is obtained.

[0205] (Additive (F))

[0206] The epoxy resin composition of the present embodiment may further include other additives (F) in addition to the alcohol (C), film-forming polymer (D), and filler (E) described above.

[0207] As an additive (F), for the purpose 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 low-stress agent, a flame retardant, and a leveling agent may be used.

[0208] Additive (F) may be used as a single type or in combination of two or more types.

[0209] The content of the additive (F) can be appropriately set according to the desired performance and is not particularly limited, but with respect to the entire epoxy resin composition of the present embodiment, it is preferable to have 0.00001 mass% or more, more preferable to have 0.0001 mass% or more, and even more preferable to have 0.001 mass% or more. In addition, the content of the additive (F) with respect to the entire epoxy resin composition of the present embodiment is preferably less than 20 mass%, more preferable to have less than 15 mass%, more preferable to have less than 10 mass%, even more preferable to have less than 8 mass%, even more preferable to have less than 7 mass%, particularly preferable to have less than 6 mass%, even more preferable to have less than 5 mass%, very more preferable to have less than 3 mass%, and very particularly preferable to have less than 2 mass%.

[0210] Reactive Diluent

[0211] The reactive diluent can lower the viscosity of the epoxy resin composition of the present embodiment and react with the latent curing agent (B) to become part of the cured product.

[0212] Reactive diluents may be compounds containing one or more glycidyl groups within their molecules. Examples of reactive diluents include butylglycidyl ether, diglycidylaniline, N,N'-glycidyl-o-toluidine, phenylglycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether, but are not limited to the following.

[0213] In addition, epoxy resins that can be used as the reactive diluents described above may be cited. That is, as reactive diluents, examples include 2-ethylhexylglycidyl ether, cyclohexanedimethanol 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)diode, Glycidylamine-type epoxy resins such as 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane, tetraglycidylbis(aminomethyl)cyclohexane, 1,3-diglycidyl-5-methyl-5-ethylhydantoin-type epoxy resin, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane-type epoxy resin, phenylglycidyl ether, cresylglycidyl ether, ps-butylphenylglycidyl ether, p-tert-butylphenylglycidyl ether, o-phenylphenolglycidyl ether, p-phenylphenolglycidyl ether, N-glycidylphthalimide, n-butylglycidyl ether, 2-ethylhexylglycidyl ether, α-pineneoxide, allylglycidyl ether, Various epoxy resins such as 1-vinyl-3,4-epoxycyclohexane, 1,2-epoxy-4-(2-methyloxyranyl)-1-methylcyclohexane, 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane, and neodecanoic acid glycidyl ester can also be used.

[0214] In addition, various monoepoxy compounds or polyhydric alcohol glycidyl ether compounds can be used as reactive diluents, but since these have only one functional group (epoxy group, glycidyl group) per molecule that contributes to the reaction with the latent curing agent (B) and cannot form three-dimensional crosslinks during curing, there is a tendency not to make the glass transition temperature (Tg) or toughness of the cured product of the epoxy resin composition of the present embodiment sufficient. Therefore, as a reactive diluent, a compound containing two or more glycidyl groups per molecule is preferred because it can form three-dimensional crosslinks during curing. This tends to suppress the decrease in glass transition temperature (Tg) or toughness during curing.

[0215] Reactive diluents may be used as a single type or in combination of two or more types.

[0216] 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 it is preferably 1.0 part by mass or more and 30 parts by mass or less per 100 parts by mass of epoxy resin (A). By having a content of 1.0 part by mass or more of the reactive diluent, the increase in viscosity of the epoxy resin composition at room temperature is suppressed, so when the epoxy resin composition of the present embodiment is used as a film for burying wiring, good buryability tends to be obtained. In addition, the decrease in glass transition temperature (Tg) or toughness during the curing of the epoxy resin composition of the present embodiment tends to suppress the occurrence and progression of fillet cracks.

[0217] Meanwhile, the content of the reactive diluent is 30 parts by weight or less per 100 parts by weight of the epoxy resin (A), thereby suppressing the decrease in adhesion to the substrate and tending to suppress delamination during the moisture absorption reflow test.

[0218] In addition, the content of the reactive diluent may be adjusted to a high amount to suppress the increase in viscosity of the epoxy resin composition that occurs when the filler (E) is highly filled.

[0219] Solvent

[0220] Examples of solvents include, but are not limited to, halogenated 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; etc.

[0221] In addition, solvents such as ethyl acetate, dimethylformamide, methylcellosolve, and propylene glycol monomethyl ether may be used in combination with the above solvent. Among these, it is preferable to use ethyl acetate as an ester in terms of the solubility and boiling point of the epoxy resin composition of the present embodiment.

[0222] As the solvent combined with ethyl acetate, an aromatic solvent having a boiling point of 120°C or lower, such as toluene, is preferred. In addition, the solvent may be used alone or in combination of two or more types.

[0223] Thermoplastic Polymers

[0224] Examples of thermoplastic polymers include, but are not limited to, polyamide resins, polyimide, polyester resins, polyurethane resins, acrylic resins, vinyl carboxylate esters, and polyether resins. Among these, acrylic resins are preferred, and vinyl carboxylate esters are more preferred. In addition, the thermoplastic polymer may be used as a single type or in combination of two or more types.

[0225] In addition, as for the acrylic resin, an acrylic resin having a glass transition temperature (Tg) of 25°C or lower is preferred, and one or more resins selected from the group consisting of hydroxyl group-containing acrylic resin, carboxyl group-containing acrylic resin, acid anhydride group-containing acrylic resin, epoxy group-containing acrylic resin, isocyanate group-containing acrylic resin, and urethane group-containing acrylic resin are more preferred, and a phenolic hydroxyl group-containing acrylic resin is even more preferred. Here, "acrylic resin" refers to a resin containing a (meth)acrylate structure, and in these resins, the (meth)acrylate structure may be included in the main chain or in the side chain.

[0226] 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 the number average molecular weight in polystyrene equivalent measured using GPC (gel permeation chromatography).

[0227] In addition, when the acrylic resin has functional groups, the functional group equivalent is preferably 1,000 or more and 50,000 or less, more preferably 2,500 or more and 30,000 or less.

[0228] The vinyl carboxylate ester may include a monomer copolymerizable with the vinyl carboxylate ester as a monomer unit. Examples of such monomers include allyl carboxylate esters and alkyl (meth)acrylate esters, and specifically, allyl acetate, methyl (meth)acrylate, and ethyl (meth)acrylate.

[0229] Stabilizer

[0230] As a stabilizer, materials that improve storage stability may be used, and are not limited to the following, but examples include boric acid and cyclic boric acid ester compounds.

[0231] A cyclic boric acid ester compound is one in which boron is included in a cyclic structure. As a cyclic boric acid ester compound, 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinan) is preferred.

[0232] In addition, one type of stabilizer may be used alone, or two or more types may be used in combination.

[0233] Liquid Low-Stress Agent

[0234] Examples of liquid low-stress agents include, but are not limited to, organic rubbers such as polyalkylene glycols and their amine modified products, polybutadiene, and acrylonitrile; silicone rubbers such as dimethylsiloxane; and silicone oil.

[0235] In addition, liquid low-stress agents may be used alone or in combination of two or more types.

[0236] The content of the liquid low-stress agent is not particularly limited, but is preferably 5.0 parts by mass or more and 40 parts by mass or less with respect to the mass (100 parts by mass) of the epoxy resin (A), and more preferably 10 parts by mass or more and 20 parts by mass or less.

[0237] Flame retardant

[0238] Examples of flame retardants include, but are not limited to, bromine-based flame retardants, phosphorus-based flame retardants, and inorganic flame retardants.

[0239] Bromine-based flame retardants are not limited to the following, but examples include tetrabromophenol.

[0240] Phosphorus-based flame retardants are not limited to the following, but examples include 9,10-dihydro-9-oxa-10-phosphanathrene-10-oxide and its epoxy derivatives, triphenylphosphine or its derivatives, phosphate esters, condensed phosphate esters, phosphazene compounds, etc.

[0241] Examples of nitrogen-based flame retardants include, but are not limited to, guanidine-based flame retardants, triazine structure-containing phenols, melamine polyphosphate, and isocyanuric acid.

[0242] Examples of inorganic flame retardant compounds include, but are not limited to, magnesium hydroxide and aluminum hydroxide. Among inorganic flame retardant compounds, magnesium hydroxide is preferred from the perspective of heat resistance.

[0243] In addition, one type of flame retardant may be used alone, or two or more types may be used in combination.

[0244] 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 with respect to the mass (100 parts by mass) of the epoxy resin (A), and more preferably 10 parts by mass or more and 100 parts by mass or less.

[0245] Leveling System

[0246] As leveling agents, examples include silicone-based leveling agents and acrylic-based leveling agents, although not limited to the following.

[0247] In addition, one type of leveling agent may be used alone, or two or more types may be used in combination.

[0248] [Adhesive Film]

[0249] The adhesive film of the present embodiment has a support and a resin layer comprising an epoxy resin composition of the present embodiment on the support.

[0250] As a support, examples include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, and polyimide, and furthermore, metal foils such as release paper, copper foil, and aluminum foil, and these may be subjected to release treatment in addition to mat treatment and corona treatment. The thickness of the support is preferably 10 μm or more and 150 μm or less.

[0251] From the perspective of reliability, it is preferable that the resin layer contains 50 mass% or more and 100 mass% or less of the epoxy resin composition of the present embodiment. The resin layer may also contain conductive particles.

[0252] The adhesive film of the present embodiment can be used as an adhesive film for forming a build-up layer of a printed circuit board or as an adhesive film for an insulating layer of a semiconductor chip package.

[0253] The printed circuit board of the present embodiment comprises a cured product of the adhesive film, and the semiconductor chip package of the present embodiment comprises a cured product of the adhesive film.

[0254] The semiconductor device of the present embodiment comprises the printed circuit board and / or semiconductor chip package.

[0255] [Method for preparing an epoxy resin composition]

[0256] The epoxy resin composition of the present embodiment can be prepared by mixing the above-described epoxy resin (A) and latent curing agent (B), and, if necessary, other curing agents other than the latent curing agent (B), alcohol (C), film-forming polymer (D), filler (E), additive (F), etc. The mixing method may be any method known in the art. For example, methods may include heating to a temperature that does not cause curing and mixing, or dissolving or dispersing each resin composition in an organic solvent to form a varnish.

[0257] [Method for manufacturing adhesive film]

[0258] As a method for manufacturing an adhesive film, for example, an epoxy resin (A), a latent curing agent (B), and, if necessary, other curing agents other than the latent curing agent, an alcohol (C), a film-forming polymer (D), a filler (E), and an additive (F) are dissolved in a solvent by heating or uniformly dispersed, and then, if necessary, cooled to 50°C or lower to obtain a varnish of an epoxy resin composition. The concentration of solids in the varnish is not particularly limited, but is preferably 30 mass% or more and 80 mass% or less.

[0259] Examples of solvents include, but are not limited to the following: halogenated solvents such as dichloromethane and chloroform; aromatic solvents such as benzene, toluene, xylene, and mesitylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, aliphatic ketones such as acetone, aromatic ketones such as acetophenone; etc. In addition, other solvents such as ethyl acetate, dimethylformamide, methyl cellosolve, and propylene glycol monomethyl ether may be used together. Among these, it is preferable to use ethyl acetate in combination as an other solvent from the perspective of the solubility and boiling point of the epoxy resin composition. As the aforementioned solvent combined with ethyl acetate, it is preferable to use an aromatic solvent with a boiling point of 120°C or lower, such as toluene. In addition, the solvent may be used as a single type or in combination of two or more types.

[0260] In the manufacturing process of the adhesive film of the present embodiment, it is preferable to dissolve the epoxy resin composition of the present embodiment in a mixed solvent containing ethyl acetate at room temperature. Dissolving at room temperature as described herein means that when mixed with a solid content concentration of 10 mass%, a solution state is obtained at room temperature, and a state in which substantially no solid content is present is maintained for at least one day, preferably at least 30 days.

[0261] The adhesive film of the present embodiment can be manufactured by applying a varnish of the epoxy resin composition onto a support film and removing the solvent by heating and drying to form a film. By this, a semi-cured adhesive film is obtained. 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.

[0262] In the view that the adhesive film of the present embodiment can be made smaller, it is preferable that the thickness be 200 μm or less. More preferably, it is 120 μm or less, even more preferably 70 μm or less, and even more preferably 20 μm or less. In addition, in the view that embedding and insulation properties can be secured, it is preferable that the thickness be 5 μm or more. More preferably, it is 7 μm or more, and even more preferably 10 μm or more.

[0263] The above heating and drying conditions are such that the heating temperature is 60°C or higher and 150°C or lower, preferably 90°C or higher and 120°C or lower, and the heating time is 1 minute or higher and 20 minutes or lower, preferably 2 minutes or higher and 10 minutes or lower.

[0264] If the heating and drying conditions are within this range, the solvent remaining in the resulting adhesive film is sufficiently removed, and the volatile content in the adhesive film can be reduced to 1 mass% or less. In addition, the curing of the adhesive film by film formation can be suppressed, so when the adhesive film of this embodiment is laminated and used on a predetermined inner layer circuit board, the inter-wire filling ability can be secured.

[0265] In the manufacturing process of the adhesive film, as a method for coating a varnish containing the epoxy resin composition of the present embodiment onto a support, known methods may be applied and are not particularly limited, but examples include a bar coater, a rip coater, a die coater, a roll coater, a doctor blade coater, etc.

[0266] [Printed Wiring Board]

[0267] The printed circuit board of the present embodiment includes a layer formed by curing the adhesive film of the present embodiment described above. When manufacturing a printed circuit board using the adhesive film, the adhesive film manufactured by the above method is bonded to a patterned inner layer circuit board, and laminating is performed while applying pressure and heating from the support side. The inner layer circuit surface may be pre-treated. Laminating is performed under atmospheric pressure or reduced pressure, in a batch manner or continuously on a roll, but it is preferable to laminate both sides simultaneously. At this time, the laminating conditions are preferably a compression temperature of 70°C to 150°C and a compression pressure of 0.1 to 60 MPa. In addition, from the perspective of void reduction, it is preferable to laminate under reduced pressure of 2 KPa or less. From the perspective of maintaining the thickness of the adhesive film after compression, the compression pressure is preferably 40 MPa or less.

[0268] After laminating, the substrate is cooled to room temperature, then peeled off from the adhesive film, and the resin layer laminated on the inner layer circuit board is heat-cured. As for the curing conditions, a curing temperature of 130 to 250°C and a curing time of 30 to 180 minutes are preferred.

[0269] Next, a location that becomes a by-hole is formed using a laser such as a carbon dioxide laser, and then roughening treatment is performed with an oxidizing agent such as permanganate, dichromate, or ozone for the purpose of removing smear and improving the adhesion of the plating. After that, a conductor circuit is selectively formed on the resin layer of the border layer by electroless plating or electrolytic plating, and an outer layer circuit is formed by simultaneously forming a conductor layer on the inner wall of the by-hole. After that, the adhesion between the conductor layer and the resin layer can be improved by performing an annealing treatment at a temperature in the range of 150 to 250°C for a time in the range of 30 to 60 minutes. By repeating the above manufacturing method using the adhesive film of the present embodiment on the conductor circuit layer obtained in this way, a multi-stage build-up layer can be formed to manufacture a multi-layer printed circuit board.

[0270] When heat curing, it is preferable to perform the process under conditions of 220°C or lower in order to volatilize organic compounds and also inhibit decomposition.

[0271] [Semiconductor chip package, semiconductor device]

[0272] The semiconductor chip package of the present embodiment comprises a cured product of the adhesive film.

[0273] The semiconductor device of the present embodiment comprises the printed circuit board and / or semiconductor chip package.

[0274] [How to use adhesive film]

[0275] It is preferable to manufacture a predetermined laminate or semiconductor chip package by laminating the adhesive film of the present embodiment under conditions of a compression pressure of 40 MPa or less, as described in [Printed Circuit Board] above, and then performing heat curing under heating conditions of a temperature of 220°C or less.

[0276] The compression pressure is more preferably 20 MPa or less, and even more preferably 10 MPa or less.

[0277] The temperature of the heat curing is more preferably 200°C or lower, and even more preferably 180°C or lower.

[0278] By setting the compression pressure to 40 MPa or less, a practically sufficient thickness can be secured after compression.

[0279] In addition, by keeping the temperature of the heat curing 220°C or lower, the organic compound can be sufficiently volatilized, and furthermore, the decomposition of the resin layer of the adhesive film can be prevented.

[0280] Examples

[0281] The embodiments of the present invention will be described in more detail below with reference to examples and comparative examples, but these are illustrative and the present invention is not limited by the following examples and comparative examples. That is, those skilled in the art may implement the present invention by making various modifications to the embodiments shown below.

[0282] In addition, unless otherwise specifically noted below, "part" is based on mass.

[0283] In addition, the values ​​of various manufacturing conditions or evaluation results in the following examples have the meaning of preferred values ​​for upper or lower limits in the embodiments of the present invention. The preferred range has the meaning of preferred values ​​for the upper or lower limits mentioned above, and the preferred range may be a range defined by a combination of the values ​​of the upper or lower limits mentioned above and the values ​​of the following examples or values ​​among the examples.

[0284] [Preparation of constituent materials of epoxy resin composition]

[0285] The following describes examples of the preparation of constituent materials used in the epoxy resin compositions of the examples and comparative examples described below.

[0286] ((Preparation Example 1) Preparation of Curing Agent 1 for Epoxy Resin)

[0287] One equivalent of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation: trade name "jER828EL") and one equivalent of 2-ethyl-4-methylimidazole (calculated as active hydrogen) were reacted at 80°C in a 1:1 mixed solvent of n-butanol and toluene. Subsequently, the excess amine was removed by distillation together with the solvent under reduced pressure to obtain a block-type curing agent for epoxy resin that is solid at 25°C.

[0288] Subsequently, the above-mentioned block-shaped epoxy resin curing agent is ground with a jet mill and further classified using a classifier, so that the specific surface area value is 3.63 m² 2 A curing agent for epoxy resin 1 was obtained, which is a curing agent for epoxy resin having a distribution of / g, average particle size D50 of 2.50㎛, and D99 / D50 of 5.4.

[0289] ((Preparation Example 2) Preparation of Curing Agent 2 for Encapsulated Epoxy Resin)

[0290] 100 parts by mass of the curing agent 1 for the epoxy resin was uniformly dispersed in 200 parts by mass of hexane, 30 parts by mass of an encapsulating agent (manufactured by Doso Co., Ltd.: product name "MR-400") was added, and the reaction was carried out for 3 hours while stirring at 50°C to obtain an encapsulated curing agent 2 for the epoxy resin that is solid at 25°C.

[0291] IR measurements were performed on the obtained curing agent 2 for epoxy resin, and in the shell, the wavenumber was 1630 cm⁻¹ -1 Over 1680cm -1 Coupler (x) absorbing infrared radiation below, wavenumber 1680 cm -1 Over 1725cm -1 A coupler (y) absorbing infrared radiation below, wavenumber 1730 cm -1 Over 1755cm -1 A peak originating from the coupler (z) that absorbs infrared radiation was identified.

[0292] ((Preparation Example 3) Preparation of Curing Agent 3 for Epoxy Resin)

[0293] Using the epoxy resin curing agent 1 obtained in the above (Preparation Example 1), a Cryptoron Orb manufactured by Earth Technica Co., Ltd. is used, and under an environment of temperature 10°C and humidity 30%, a rotation speed of 13,500 rpm, a feed speed of 10 kg / hr, and an airflow of 3 m³ 3 Shape correction treatment was performed at a rate of / min. A cyclone-type collector and a bag filter were attached to the classifier, and a classification operation was performed, resulting in a specific surface area value of 2.67m². 2 A curing agent for epoxy resin 3 was obtained, which is a curing agent for epoxy resin having a particle size distribution of / g, D50 3.1㎛, and D99 / D50 4.5.

[0294] ((Preparation Example 4) Preparation of Curing Agent 4 for Encapsulated Epoxy Resin)

[0295] 100 parts by mass of the curing agent 3 for the epoxy resin was uniformly dispersed in 200 parts by mass of hexane, 20 parts by mass of an encapsulating agent (manufactured by Doso Co., Ltd.: product name "Coronate T100") was added, and the reaction was continued for 3 hours while stirring at 50°C to obtain an encapsulated curing agent 4 for the epoxy resin that is solid at 25°C.

[0296] IR measurements were performed on the obtained curing agent 4 for epoxy resin, and in the shell, the wavenumber was 1630 cm⁻¹ -1 Over 1680cm -1 Coupler (x) absorbing infrared radiation below, wavenumber 1680 cm -1 Over 1725cm -1 A coupler (y) absorbing infrared radiation below, wavenumber 1730 cm -1 Over 1755cm -1 A peak originating from the coupler (z) that absorbs infrared radiation was identified.

[0297] ((Preparation Example 5) Preparation of Curing Agent 5 for Epoxy Resin)

[0298] One equivalent of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation: trade name "jER828EL") and one equivalent of 2-methylimidazole (calculated based on active hydrogen) were reacted at 80°C in a 1:1 mixed solvent of n-butanol and toluene. Subsequently, the excess imidazole and solvent were completely removed by distillation under reduced pressure to obtain a block-type curing agent for epoxy resin that was solid at 25°C. The obtained curing agent for epoxy resin was ground using a turbo mill to obtain a specific surface area of ​​0.36 m² 2 A curing agent 5 for epoxy resin was obtained, with a sieve load average particle size D50 of 9.80㎛ and a D99 / D50 of 4.2.

[0299] ((Preparation Example 6) Preparation of film-forming polymer D-1)

[0300] 170 parts by mass of a biphenyl-type epoxy resin (manufactured by Mitsubishi Chemical Corporation: trade 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 the reaction was carried out at 170°C for 2 hours while stirring under a nitrogen atmosphere. After the reaction was finished, the temperature was raised to 200°C over 3 hours while removing xylene from the system, and the reaction was continued at 200°C for another 7 hours to obtain a film-forming polymer D-1 with a number average molecular weight of 22,500.

[0301] ((Preparation Example 7) Preparation of Alcohol C-1)

[0302] 50 parts by mass of bisphenol A diglycidyl ether (BADGE, Aldrich reagent, epoxy equivalent 172 g / eq), 10 parts by mass of methanol, 1 part by mass of water, and 0.005 parts by mass of trimethylammonium chloride were mixed, and the reaction was carried out at 60°C for 2 hours while stirring under a nitrogen atmosphere.

[0303] After the reaction was finished, methanol and the remaining water were removed by distillation under reduced pressure at 140°C to obtain alcohol C-1 with an alcoholic hydroxyl equivalent of about 20,000 g / eq.

[0304] [Method of evaluating characteristics]

[0305] The following describes a method for evaluating the characteristics of the resin compositions of the examples and comparative examples described below.

[0306] ((1) Evaluation of film preservation stability)

[0307] A 50% MEK (methyl ethyl ketone) solution of the epoxy resin compositions of the examples and comparative examples was prepared as a varnish. Immediately after preparing the varnish, it was coated onto a PET film to a thickness of about 50 μm using a coating machine, and then dried in an oven at 100°C for 5 minutes to obtain an adhesive film.

[0308] FT-IR measurements were performed on the obtained adhesive film, and 926 cm⁻¹ derived from epoxy groups -1 Peak (P1) and 1510 cm⁻¹ derived from the phenyl group -1 The peak ratio F1(P1 / P2) of the peak (P2) was calculated.

[0309] In addition, after storing this adhesive film at 9°C for 30 days, FT-IR measurements were performed in the same manner to calculate the peak ratio F2 (P1 / P2) after storage.

[0310] To compare the above F1 and F2, the residual peak ratio of epoxy groups ((F2 / F1)×100) was calculated. If the residual peak ratio of epoxy groups was 90% or more and 99% or more, it was evaluated as “◎”; if 70% or more and less than 90%, it was evaluated as “○”; if 50% or more and less than 70%, it was evaluated as “△”; and if less than 50%, it was evaluated as “×”.

[0311] ((2) Evaluation of landfill suitability)

[0312] On an FR-5 substrate (17cm × 34cm, thickness 0.4mm) having wiring lines / spaces of 10㎛ / 10㎛ and wiring thickness of 7㎛ as depicted by direct imaging processing using a dry film resist, the adhesive film produced in (1) above was laminated onto one side of the substrate while the PET film was attached, using a roll laminator under conditions of a compression temperature of 90℃, a compression pressure of 0.3 to 0.5MPa, and a laminating speed of 0.4m / min.

[0313] Gaps between wires where resin was not present were identified as bubbles, and the presence of bubbles was visually inspected; if no bubbles were present, it was evaluated as "○," and if they were present, as "×."

[0314] ((3) Evaluation of Flexibility)

[0315] After laminating in the above ((2) embedment test), the PET film was peeled off from the adhesive film and then compressed and cured at 175°C × 45 minutes and 40 MPa to obtain a test specimen. After curing, the specimen was placed in a downward convex state at room temperature, and when one side of the specimen, measuring 17 cm, was pressed onto a desk, the height of the other side lifted off the desk was measured.

[0316] At this time, the height from the desk was evaluated as “◎” for less than 1.0 cm, “○” for 1.0 cm or more and less than 1.5 cm, “△” for 1.5 cm or more and less than 3 cm, and “×” for 3 cm or more.

[0317] ((4) Evaluation of heat resistance)

[0318] In the test specimen prepared in the above ((3) Flexibility), a portion without bubbles was cut to a size of 0.5 cm × 0.5 cm, and the specimen was heated to a constant temperature of 288°C using a measuring instrument TMAQ400 (manufactured by TA Instrumental) and the time until expansion occurred was measured.

[0319] The time until expansion occurred was evaluated as “○” for 60 minutes or more, “△” for 45 minutes or more but less than 60 minutes, and “×” for 45 minutes or less.

[0320] ((5) Evaluation of Peel Strength)

[0321] A film-like adhesive, peeled from a PET film, was placed between an FR-5 substrate and a copper foil with a thickness of 1 / 2 oz, and compressed at 165°C for 30 minutes at 40 MPa. Subsequently, an incision of 10 mm in width and 150 mm in length was made in the copper foil on the substrate, and a 90-degree peel strength measurement was performed.

[0322] Peel strength: 1.0 kgf / cm or more was rated as “◎”, 0.8 or more but less than 1.0 kgf / cm as “○”, 0.6 or more but less than 0.8 as “△”, 0.4 or more but less than 0.6 as “×”, and less than 0.4 as “××”.

[0323] ((6) Measurement of permittivity and dielectric loss tangent)

[0324] Forty sheets of film-like adhesive peeled from PET film were stacked and cured at 180°C for 60 minutes under reduced pressure to obtain a cured product.

[0325] The obtained hardened material was cut into pieces 2 mm wide and 80 mm long to obtain test specimens. For these test specimens, the permittivity (ε) and dielectric loss tangent (tanδ) were measured at a measurement frequency of 1.0 GHz using the cavity resonance method with a cavity resonator perturbation method permittivity measuring device manufactured by Kanto Applied Electronics Development Co., Ltd. and a network analyzer E8362B manufactured by Argilent Technology Co., Ltd.

[0326] Measurements were taken on 5 test specimens, and the average value was calculated. The value of √ε×tanδ was evaluated as “◎” for less than 0.01, “○” for 0.01 or more and less than 0.012, “△” for 0.012 or more and less than 0.015, and “×” for 0.015 or more.

[0327] [Examples 1 to 10], [Comparative Examples 1, 2]

[0328] An epoxy resin composition was obtained by dissolving or uniformly dispersing component (A), component (B), component (D), other curing agent components, filler (E), and additive (F) in a solvent heated to 60°C according to the mixing ratios listed in Tables 1 and 2, then cooling to 30°C, and also mixing and uniformly dispersing component (C).

[0329] In addition, the adhesive film used for the evaluation was produced by applying the above epoxy resin composition onto a PET film with a thickness of about 50 μm using a die coater, and then drying it in an oven at 100°C for 5 minutes.

[0330] [Constituent materials of the epoxy resin composition]

[0331] Each component listed in Tables 1 and 2 below is shown below.

[0332] ((A) Epoxy resin)

[0333] A-1: Epiclone 850CRP (Bisphenol A type epoxy resin, manufactured by DIC Co., Ltd., epoxy equivalent 175g / eq)

[0334] A-2: YX4000 (Biphenyl-type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 170g / eq)

[0335] A-3: NC3000H (Biphenylaralkyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269 g / eq)

[0336] A-4: HP4710 (Naphthalene-type epoxy resin, manufactured by DIC Co., Ltd., epoxy equivalent 170g / eq)

[0337] A-5: YX7760 (Fluorine-containing epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 235g / eq)

[0338] ((B) component)

[0339] B-1: Curing agent for epoxy resin of Preparation Example 1

[0340] B-2: Curing agent for epoxy resin of Preparation Example 2 2

[0341] B-3: Curing agent for epoxy resin of Preparation Example 3 3

[0342] B-4: Curing agent for epoxy resin of Preparation Example 4 4

[0343] B-5: Curing agent for epoxy resin of Preparation Example 5 5

[0344] (Other curing agent components)

[0345] DMAP: 4-Dimethylaminopyridine (Manufactured by Koei Chemical Co., Ltd., moisture content 1.7%, specific surface area 0.1m² 2 / g, average particle size D50 is 15.4㎛, D99 / D50 is 6.4)

[0346] LA7054: (Phenol-novolak type resin, manufactured by DIC Co., Ltd., hydroxyl equivalent 125g / eq)

[0347] LA3018: (Phenol-novolak type resin, manufactured by DIC Co., Ltd., hydroxyl group equivalent 150g / eq)

[0348] EXB9460S: (Activated ester resin, manufactured by DIC Co., Ltd., ester equivalent 223g / eq)

[0349] HPC8000: (Activated ester resin, manufactured by DIC Co., Ltd., ester equivalent 223g / eq)

[0350] ((C) component)

[0351] C-1: Alcohol of Preparation Example 7

[0352] C-2: 3-Phenoxy-1-Propanol (Reagent, manufactured by Tokyo Kasei Co., Ltd.)

[0353] C-3: 3-Phenoxy-1,2-Propanediol (Reagent, manufactured by Tokyo Kasei Co., Ltd.)

[0354] ((D) Film-forming polymer)

[0355] D-1: Film-forming polymer of Preparation Example 6

[0356] D-2: YP50 (Phenoxy Resin (Manufactured by Nittetsu Chemical & Material Co., Ltd.))

[0357] ((E) component)

[0358] E-1: Aminosilane-treated synthetic spherical silica SO-C2 (manufactured by Admatex Co., Ltd.)

[0359] ((F) component)

[0360] F-1: YED216L (1,6-Hexanediol Diglycidyl Ether, manufactured by Mitsubishi Chemical Corporation)

[0361] F-2: CDMDG (1,4-cyclohexanedimethanol diglycidyl ether, manufactured by Showa Denko Co., Ltd.)

[0362]

[0363]

[0364] As shown in Tables 1 and 2, in Examples 1 to 10, an epoxy resin composition was obtained that has good storage stability after film formation, excellent embedding and curing performance of fine wiring, and compatibility between storage stability and reactivity.

[0365] This application is based on Japanese patent application filed with the Japan Patent Office on December 22, 2020 (Japanese Patent Application No. 2020-212769) and Japanese patent application filed with the Japan Patent Office on January 18, 2021 (Japanese Patent Application No. 2021-005649), the contents of which are incorporated herein by reference. Industrial applicability

[0366] The epoxy resin composition of the present invention has industrial applicability in fields such as adhesive films, printed circuit boards, semiconductor chip packages, and semiconductor devices, where multilayering, miniaturization and high-density wiring, and low dielectric loss tangent are required.

Claims

Claim 1 An epoxy resin composition comprising an epoxy resin (A) and a latent curing agent (B), wherein the latent curing agent (B) is solid at 25°C and further comprises an alcohol (C) represented by the following formula (1), wherein the alcohol (C) is contained in an amount of 0.003 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the total of the epoxy resin (A) and the latent curing agent (B), and further comprises an active ester curing agent in addition to the latent curing agent (B). (In the above formula (1), R1 to R9 are each independently 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 each be the same or different, and any of R5 to R9 selected may be combined with each other to form a ring structure, and the ring structure may be a condensation ring with a benzene ring shown in the formula.) Claim 2 An epoxy resin composition according to claim 1, wherein the potential curing agent (B) is an amine-based curing agent having an amine group. Claim 3 An epoxy resin composition according to claim 1 or 2, wherein the latent curing agent (B) has a particle size D50 with a total load fraction of 50% that is greater than 0.3㎛ and less than or equal to 10㎛, and a particle size distribution represented by the ratio (D99 / D50) of the particle size D99 with a total load fraction of 99% and the particle size D50 with a total load fraction of 50% that is 6 or less. Claim 4 In claim 1 or 2, the potential curing agent (B) is a specific surface area value (=Y(m 2 An epoxy resin composition in which the particle size D50 (=X(㎛)) of the above-mentioned cumulative fraction of 50% of the above-mentioned body load satisfies the relationship represented by the following formula (2). 4.0X-1≤Y≤8.3X-1 (2) (In the case where the above-mentioned latent curing agent (B) encapsulates the curing agent component with an encapsulating agent, the curing agent component before encapsulation satisfies the above-mentioned formula (2).) Claim 5 In claim 1, the latent curing agent (B) has a core (c) which is a curing agent component and a shell (s) covering the core (c), and the shell (s) has at least a wavenumber of 1630 cm -1 Over 1680cm -1 A coupler (x) that absorbs infrared radiation below, and a wavenumber of 1680 cm -1 Over 1725cm -1 A coupler (y) that absorbs infrared radiation below, and a wavenumber of 1730 cm -1 Over 1755cm -1 An epoxy resin composition having a linker (z) that absorbs infrared rays. Claim 6 An epoxy resin composition according to claim 1, wherein R1 in the above formula (1) is a hydroxyl group. Claim 7 An epoxy resin composition according to claim 1, wherein the alcohol (C) is contained in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the total of the epoxy resin (A) and the latent curing agent (B). Claim 8 An epoxy resin composition according to any one of claims 1 and 5 to 7, wherein, in addition to the potential curing agent (B), one or more curing agents selected from the group consisting of phenolic curing agents, amine-based curing agents, acid anhydride-based curing agents, and thiol-based curing agents. Claim 9 An epoxy resin composition comprising a film-forming polymer (D) further comprising, in any one of claims 1 and 5 to 7. Claim 10 An epoxy resin composition comprising a filler (E) further comprising any one of claims 1 and 5 to 7. Claim 11 An epoxy resin composition in which the filler (E) is an inorganic filler in claim 10. Claim 12 An epoxy resin composition comprising an additive (F) further comprising any one of claims 1 and 5 to 7. Claim 13 An adhesive film having a support and a resin layer on the support comprising an epoxy resin composition described in any one of claims 1 and 5 to 7. Claim 14 An adhesive film having a support and a resin layer comprising the epoxy resin composition described in claim 8 on the support. Claim 15 In Clause 13, an adhesive film having a thickness of 20㎛ or less. Claim 16 In paragraph 13, an adhesive film for forming a build-up layer of a printed circuit board. Claim 17 In paragraph 13, an adhesive film for an insulating layer of a semiconductor chip package. Claim 18 A printed circuit board comprising a layer of the adhesive film described in paragraph 13 that has been cured. Claim 19 A semiconductor chip package comprising a cured layer of the adhesive film described in paragraph 13. Claim 20 A semiconductor device comprising a printed circuit board having a layer of the adhesive film described in claim 13 and / or a semiconductor chip package having a layer of the adhesive film described in claim 13. Claim 21 A method of using an adhesive film, wherein the adhesive film described in paragraph 13 is laminated under conditions of a compression pressure of 40 MPa or less, and then a laminated material or a semiconductor chip package is manufactured under heating conditions of a temperature of 220°C or less.

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