CN116615509A - Epoxy resin composition, adhesive film, printed circuit board, semiconductor chip package, semiconductor device, and method for using adhesive film - Google Patents

Abstract

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 ℃.

Description

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

Technical Field

The 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

Conventionally, thermosetting resin compositions containing epoxy resins and the like which are excellent in adhesion and exhibit high reliability have been used as adhesives for semiconductor devices and adhesives for printed wiring boards. As the constituent components of the thermosetting resin composition, a curing agent such as an epoxy resin, a phenolic resin reactive with the epoxy resin, and a curing catalyst that promotes the reaction between the epoxy resin and the curing agent are generally used.

In recent years, semiconductor devices and printed circuit boards have been improved in performance, and they have been multilayer using stacked layers, and miniaturization and higher density of wiring have been demanded, and further, low dielectric loss tangent have been demanded. In addition, with the multilayer mounting of semiconductor elements and printed circuit boards, adhesives curable under low temperature conditions are required.

Various improvements have been made to this.

For example, patent document 1 discloses an epoxy resin composition for forming an insulating layer of a multilayer printed wiring board, which contains (a) an epoxy resin, (B) an active ester compound as a curing agent for the epoxy resin, (C) a cresol novolac resin containing triazine, and (D) an inorganic filler having an average particle diameter of 1 μm or less, wherein the content of the inorganic filler having an average particle diameter of 1 μm or less is 48 mass% or more and 85 mass% or less when the nonvolatile component in the epoxy resin composition is 100 mass%. Patent document 1 describes that: the epoxy resin composition exhibits high adhesion to a plated conductor, and can achieve a low linear expansion coefficient and a low dielectric loss tangent of an insulating layer.

Further, patent document 2 discloses an epoxy resin composition containing (a) an epoxy resin, (B) a curing agent, and (C) an inorganic filler surface-treated with a specific surface-treating agent, as a resin composition for printed wiring which exhibits good reflow characteristics in a component mounting process even when a printed wiring board is thin.

Prior art literature

Patent literature

Patent document 1: japanese patent No. 6190092

Patent document 2: japanese patent laid-open No. 2020-045501

Disclosure of Invention

Problems to be solved by the invention

However, the epoxy resin compositions disclosed in patent documents 1 and 2 have the following problems: the storage stability after the film is formed is insufficient, the filling property of the micro wiring is poor, the warpage of the substrate is poor due to the high temperature required for curing, and the curing performance is not sufficient in practical use, and there is room for improvement of these properties.

Accordingly, an object of the present invention is to provide an epoxy resin composition having excellent storage stability after forming a film, excellent filling property of micro wiring, excellent warpage of a substrate, and excellent curing property; an adhesive film, a printed wiring board, a semiconductor chip package, a semiconductor device, and the like having a resin layer containing the aforementioned epoxy resin composition.

Solution for solving the problem

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present invention has been accomplished by using a latent curing agent (B) satisfying specific conditions in a resin composition containing an epoxy resin (a) and a latent curing agent (B) to solve the above-mentioned problems.

Namely, the present invention is as follows.

[ 1 ] an epoxy resin composition comprising an epoxy resin (A) and a latent curing agent (B),

the latent curing agent (B) is solid at 25 ℃.

[ 2 ] the epoxy resin composition according to the above [ 1 ], which further comprises an alcohol (C) represented by the following formula (1).

In the above formula (1)，R ₁ ～R ₉ Each independently is one selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkyl group, an aromatic group, a substituent containing a hetero atom, and a substituent containing a halogen atom, R ₁ ～R ₉ Are optionally identical or different from one another and are selected from R ₅ ～R ₉ Optionally bonded to each other to form a ring structure, which is optionally a condensed ring with the benzene ring shown in the formula.

The epoxy resin composition according to [ 1 ] or [ 2 ], wherein the latent curing agent (B) is an amine curing agent having an amine moiety.

The epoxy resin composition according to any one of the above [ 1 ] to [ 3 ], wherein,

the particle size distribution represented by the ratio (D99/D50) of the particle size D99 of the undersize cumulative fraction of 99% to the particle size D50 of the undersize cumulative fraction of 50% of the latent curing agent (B) is 6 or less, wherein the particle size D50 of the undersize cumulative fraction of 50% exceeds 0.3 μm and is 10 μm or less.

The epoxy resin composition according to any one of the above [ 1 ] to [ 4 ], wherein the specific surface area value (=Y (m) of the latent curing agent (B) ² /g)) and the particle diameter d50 (=x (μm)) of the undersize cumulative fraction 50% satisfy the relationship represented by the following formula (2).

4.0X-1≤Y≤8.3X-1 (2)

(when the latent curing agent (B) is a latent curing agent obtained by encapsulating a curing agent component with an encapsulating agent, the curing agent component before encapsulation satisfies the above formula (2))

The epoxy resin composition according to any one of the above [ 1 ] to [ 5 ], wherein the latent curing agent (B) has a core (c) as a curing agent component and a shell(s) covering the core (c),

the shell(s) has an absorption wave number of 1630cm ^-1 Above and 1680cm ^-1 The following infrared bonding group (x), absorption wavenumber 1680cm ^-1 Above and 1725cm ^-1 The following infrared bonding group (y) and wave number absorption1730cm ^-1 Above 1755cm ^-1 The following infrared bonding group (z).

The epoxy resin composition according to any one of the above [ 2 ] to [ 6 ], wherein R in the above formula (1) ₁ Is hydroxyl.

The epoxy resin composition according to any one of the above [ 2 ] to [ 7 ], wherein the alcohol (C) is contained in an amount of 0.001 to 20 parts by mass based on 100 parts by mass of the total of the epoxy resin (A) and the latent curing agent (B).

The epoxy resin composition according to any one of the above [ 2 ] to [ 8 ], wherein the alcohol (C) is contained in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the total of the epoxy resin (A) and the latent curing agent (B).

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

The epoxy resin composition according to any one of the above [ 1 ] to [ 10 ], which further comprises a film-forming polymer (D).

The epoxy resin composition according to any one of the above [ 1 ] to [ 11 ], which further comprises a filler (E).

The epoxy resin composition according to any one of the above [ 1 ] to [ 12 ], wherein the filler (E) is an inorganic filler.

The epoxy resin composition according to any one of the above [ 1 ] to [ 13 ], which further comprises an additive (F).

[ 15 ] an adhesive film comprising a support and, on the support, a resin layer comprising the epoxy resin composition according to any one of [ 1 ] to [ 14 ].

The adhesive film according to [ 16 ] above, which has a thickness of 20 μm or less.

The adhesive film according to [ 15 ] or [ 16 ], which is an adhesive film for forming a laminate of printed wiring boards.

The adhesive film according to [ 15 ] or [ 16 ], which is an adhesive film for an insulating layer of a semiconductor chip package.

[ 19 ] A printed wiring board comprising a layer obtained by curing the adhesive film described in the foregoing [ 15 ] or [ 16 ].

[ 20 ] A semiconductor chip package comprising a layer obtained by curing the adhesive film described in [ 15 ] or [ 16 ].

The semiconductor device of [ 21 ] comprising the printed circuit board of [ 19 ] and/or the semiconductor chip package of [ 20 ].

The method for using the adhesive film of [ 22 ], wherein the adhesive film of [ 15 ] or [ 16 ] is laminated under a pressure of 40MPa or less, and thereafter a laminate or a semiconductor chip package is produced under a heating condition at a temperature of 220 ℃ or less.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, an epoxy resin composition which has excellent storage stability after being formed into a film, excellent filling property and curing property of a micro wiring, and can achieve both storage stability and reactivity can be obtained.

Detailed Description

Hereinafter, embodiments for carrying out the present invention (hereinafter, also simply referred to as "the present embodiment") will be described in detail.

The present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment. That is, the present invention can be variously modified within a range not exceeding the gist thereof.

In the present specification, the term "to" is used in a form including values before and after the term "to" when the term is expressed with values before and after the term "to" as used herein.

[ epoxy resin composition ]

The epoxy resin composition of the present embodiment contains an epoxy resin (a) and a latent curing agent (B), and the latent curing agent (B) is solid at 25 ℃.

With the above configuration, an epoxy resin composition having good storage stability after film formation, excellent filling property of micro wiring, excellent curing performance, and excellent storage stability and reactivity can be obtained.

Further, by using the epoxy resin composition of the present embodiment, reliability can be improved for an adhesive film, a printed circuit board, a semiconductor chip package, a semiconductor device, and the like, in which multilayering, miniaturization and high density of wiring, low dielectric loss tangent, and the like are required.

(epoxy resin (A))

The epoxy resin composition of the present embodiment contains an epoxy resin (a).

The epoxy resin (a) is not particularly limited, and various known epoxy resins can be appropriately selected and used.

The epoxy resin (a) may be used alone or in combination of 1 or more than 2.

Examples of the epoxy resin (a) include, but are not limited to, difunctional epoxy resins such as 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, phenyl benzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy resin, methylhydroquinone type epoxy resin, dibutyl hydroquinone type epoxy resin, resorcinol type epoxy resin, methylresorcinol type epoxy resin, catechol type epoxy resin, and N, N-diglycidyl aniline type epoxy resin.

Examples of the epoxy resin (a) include trifunctional epoxy resins such as N, N-diglycidyl aminobenzene type epoxy resin, ortho (N, N-diglycidyl amino) toluene type epoxy resin, and triazine type epoxy resin; tetrafunctional epoxy resins such as tetraglycidyl diaminodiphenylmethane type epoxy resin and diaminobenzene type epoxy resin; phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type epoxy resins, dicyclopentadiene type epoxy resins, naphthol aralkyl type epoxy resins, brominated phenol novolac type epoxy resins, and the like.

Further, examples of the epoxy resin (a) include diglycidyl ethers such as (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane diglycidyl ether, dicyclopentadiene type diglycidyl ether; triepoxy resins such as trimethylolpropane triglycidyl ether and glycerol triglycidyl ether.

Examples of the epoxy resin (a) include alicyclic epoxy resins such as vinyl (3, 4-cyclohexene) dioxide and 2- (3, 4-epoxycyclohexyl) -5, 1-spiro- (3, 4-epoxycyclohexyl) m-dioxane; hydantoin-type epoxy resins such as 1, 3-diglycidyl-5-methyl-5-ethylhydantoin; and epoxy resins having a silicone skeleton such as 1, 3-bis (3-glycidoxypropyl) -1, 3-tetramethyldisiloxane.

Examples of the epoxy resin (a) include glycidyl amine type epoxy resins such as 2-ethylhexyl glycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, hydrogenated bisphenol a type epoxy resins, silicone modified epoxy resins, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentadiene type diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, vinyl (3, 4-cyclohexene) dioxide, 2- (3, 4-epoxycyclohexyl) -5, 1-spiro- (3, 4-epoxycyclohexyl) m-dioxane, and tetraglycidyl bis (aminomethyl) cyclohexane; 1, 3-diglycidyl-5-methyl-5-ethylhydantoin type epoxy resin, 1, 3-bis (3-glycidoxypropyl) -1, 3-tetramethyldisiloxane type epoxy resin, phenyl glycidyl ether, tolyl glycidyl ether, p-sec-butylphenyl glycidyl ether, phenylethane, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide, N-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α -pinene oxide, allyl glycidyl ether, 1-vinyl-3, 4-epoxycyclohexane, 1, 2-epoxy-4- (2-methylethyl) -1-methylcyclohexane, 1, 3-bis (3-glycidoxypropyl) -1, 3-tetramethyldisiloxane, glycidyl neodecanoate, and the like can also be used as various epoxy resins as reactive diluents.

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

In the case of using a liquid epoxy resin and a solid epoxy resin in combination, the mass ratio thereof (liquid epoxy resin: solid epoxy resin) is not particularly limited, and is preferably in the range of 1:0.1 to 1:6. By setting the mass ratio of the liquid epoxy resin to the solid epoxy resin to the above range, the following effects can be obtained: (i) In the adhesive film having the support and the resin layer and using the epoxy resin composition of the present embodiment for the resin layer, moderate adhesiveness can be obtained; (ii) When the adhesive film is used in the form of the adhesive film, sufficient flexibility can be obtained, and the handleability can be improved; and (iii) a cured product having sufficient breaking strength can be obtained.

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

The content of the epoxy resin (a) in the epoxy resin composition of the present embodiment is not particularly limited, and is preferably 2.5 mass% or more, more preferably 5 mass% or more, and even more preferably 10 mass% or more, from the viewpoint of curability, depending on the desired performance of the epoxy resin of the present embodiment. From the viewpoint of film formability, the content is preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.

(latent curing agent (B))

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

The latent curing agent (B) is a solid at ordinary temperature (25 ℃).

The epoxy resin composition of the present embodiment contains the latent curing agent (B) which is solid at normal temperature (25 ℃) and thus has improved stability at room temperature and good reactivity with the epoxy resin (a). In addition, in the case of using a curing agent other than the latent curing agent (B) in combination, a curing catalyst can be formed, so that it is preferable.

The latent curing agent (B) which is solid at normal temperature (25 ℃) is preferably an amine curing agent having an amine moiety.

The term "amine moiety" refers to an organic derivative of ammonia, and is a functional group that functions as a base.

As the latent curing agent (B), an amine curing agent having an amine moiety is used, whereby an effect of obtaining high reactivity at a predetermined temperature can be obtained.

The latent curing agent (B) is not limited to the following, and examples thereof include imidazoles, imidazole adducts, amine adducts, and encapsulated substances thereof.

Specifically, AMICURE PN-23J, PN-40J, MY-24 (manufactured by Weisu Fine science and technology Co., ltd.); FUJICURE FXR-1020, FXR-1030 (manufactured by Fuji chemical industries, ltd.), etc.

The latent curing agent (B) may be used alone or in combination of 1 or more than 2.

Further, from the viewpoint of obtaining a homogeneous cured product of the epoxy resin composition of the present embodiment and from the viewpoint of preventing aggregation of particles of the latent curing agent (B) with each other and securing good physical properties of the cured product of the epoxy resin composition, the latent curing agent (B) preferably contains particles having a particle diameter D50 of more than 0.3 μm and 10 μm or less, more preferably 1 μm or more and 8 μm or less, still more preferably 1.5 μm or more and 5 μm or less, of which the cumulative fraction under the screen is 50%. If the particle diameter D50 of the latent curing agent (B) is 10 μm or less, the epoxy resin composition tends to be homogeneous, and if the particle diameter D50 exceeds 0.3 μm, aggregation between the latent curing agents tends to be suppressed, curing unevenness does not occur, and heat resistance of the cured product tends to be improved.

The method of setting the particle diameter D50 of the latent curing agent (B) to be more than 0.3 μm and 10 μm or less includes a method of mechanically pulverizing and a method of growing particles in a solvent.

The latent curing agent (B) preferably has a particle size distribution expressed by a ratio of the particle diameter D99 of 99% of the cumulative undersize fraction to the particle diameter D50 of 50% of the cumulative undersize fraction (hereinafter, abbreviated as "D99/D50") of 6.0 or less, more preferably 5.5 or less, and still more preferably 5.0 or less, from the viewpoint of suppressing aggregation of particles with each other.

By setting D99/D50 to 6.0 or less, the following tends to occur: the powder particles of the latent curing agent (B) have few coarse particles, inhibit the formation of aggregates, and inhibit the deterioration of the physical properties of the cured product of the epoxy resin composition.

The smaller the D99/D50 value, the more concentrated the particle size distribution of the latent curing agent (B), and the tendency is for the epoxy resin composition of the present embodiment to be easily obtained as a homogeneous cured product and to have good curing performance.

Further, when the value of D99/D50 is 6.0 or less, the particle size distribution of the latent curing agent (B) is narrow, and particles having a large particle diameter are unlikely to be present, so that when the epoxy resin composition of the present embodiment is formed into a film, the film tends to have excellent permeability into a predetermined gap.

The D99/D50 ratio is preferably 1.2 or more.

When the D99/D50 is 1.2 or more, a plurality of gaps between particles of the latent curing agent (B) tends to be suppressed. The D99/D50 is more preferably 1.5 or more, still more preferably 1.7 or more, still more preferably 2.0 or more.

The D99/D50 of the latent curing agent (B) can be controlled to 6 or less by a classification operation for removing coarse particles, fine particles and the like.

The latent curing agent (B) may be a single-layered particle or a core-shell type curing agent particle having a core containing a curing agent component and a shell covering the core.

The curing agent particles (curing agent components) for epoxy resins used as the cores are referred to as "curing agent particles (H)" for epoxy resins, "curing agent particles (H)" or "curing agent (H)".

The core-shell type curing agent particles as the latent curing agent (B) have a core (hereinafter also referred to as "core (c)") formed of the curing agent particles (H) for epoxy resin or the like and a shell (hereinafter also referred to as "shell(s)") covering the core (c), and the shell(s) preferably has an absorption wave number of 1630cm at least on its surface ^-1 Above and 1680cm ^-1 The following infrared bonding group (hereinafter also referred to as "bonding group (x)") and absorption wave number 1680cm ^-1 Above and 1725cm ^-1 The following infrared bonding group (hereinafter also referred to as "bonding group (y)") and absorption wave number 1730cm ^-1 Above 1755cm ^-1 The following infrared bonding group (hereinafter also referred to as "bonding group (z)").

With such a configuration, the aggregation ratio of particles of the latent curing agent (B) is reduced, and the epoxy resin composition of the present embodiment tends to be excellent in curability, storage stability, and gap permeability.

As a method for obtaining the core-shell type curing agent particles, that is, the latent curing agent (B) having the above-mentioned predetermined bonding group (x), bonding group (y) and bonding group (z) in the shell(s), there is a method of selecting a predetermined encapsulating agent for the curing agent component of the core and reacting them.

In addition, the specific surface area value (=y (m) of the latent curing agent (B) ² Preferably, the relation between the particle diameter d50 (=x (μm)) and the undersize cumulative fraction of 50% satisfies the following formula (2).

4.0X-1≤Y≤8.3X-1 (2)

In the following formula (2), X represents a particle diameter D50 (μm) of 50% of the cumulative fraction under the screen of the latent curing agent (B), and Y represents a specific surface area value (m ² /g)。

As a method for satisfying the relationship between the specific surface area value and the particle diameter D50 in the above formula (2), for example, a method for modifying the surface of the latent curing agent (B) is mentioned.

Further, by setting Y to 4.0X-1 or more, aggregation of particles of the latent curing agent (B) can be suppressed, and by setting Y to 8.3X-1 or less, stability after mixing the latent curing agent (B) with the epoxy resin (A) can be improved.

In the case where the latent curing agent (B) is a core-shell type curing agent particle having a core containing a curing agent component and a shell covering the core, for example, in the case where the curing agent component is encapsulated by an encapsulating agent, the curing agent component before encapsulation may satisfy the above formula (2).

The content of the latent curing agent (B) in the epoxy resin composition of the present embodiment is not particularly limited, and is preferably 0.2 mass% or more, more preferably 1.0 mass% or more, and even more preferably 2.0 mass% or more, from the viewpoint of reactivity, depending on desired properties. From the viewpoint of stability, it is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

(alcohol (C))

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

The inclusion of the alcohol (C) tends to improve the reactivity of the epoxy resin composition of the present embodiment while maintaining the stability.

In the formula (1), R ₁ ～R ₉ Each independently is one selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkyl group, an aromatic group, a substituent containing a hetero atom, and a substituent containing a halogen atom, R ₁ ～R ₉ Are optionally identical or different from one another and are selected from R ₅ ～R ₉ Optionally bonded to each other to form a ring structure, which is optionally a condensed ring with the benzene ring shown in the formula.

The alcohol (C) represented by the formula (1) has both excellent complexation with the latent curing agent (B) and compatibility with the epoxy resin (a) due to the aromatic ring, and has a function of improving curability of the epoxy resin composition of the present embodiment.

When the latent curing agent (B) is an amine-based curing agent that is solid at 25 ℃, the alcohol (C) does not act on the latent curing agent (B) at room temperature. However, when the temperature is equal to or higher than the predetermined temperature, the solubility of the alcohol (C) in the epoxy resin (a) is improved, and the SP value as a dissolution parameter approaches the latent curing agent (B) as an amine curing agent, and the curing property is improved by the action of easily dissolving the latent curing agent (B) 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 ℃, it is possible to achieve both the room temperature stability and the curability at warming of the epoxy resin composition of the present embodiment. This effect is more remarkably exhibited when the latent curing agent (B) is of a capsule type.

In addition, R in the formula (1) of the alcohol (C) is represented from the viewpoint of improving the complexation with the latent curing agent (B) and further improving the curability of the epoxy resin composition of the present embodiment ₁ Preferably a hydroxyl group.

Further, R in the above formula (1) is not hindered by steric hindrance from the viewpoint of the coordination of the hydroxyl group ₂ 、R ₃ And R is ₄ Preferably a hydrogen atom.

Examples of the alcohol (C) represented by the above formula (1) include, but are not limited to, 3-phenoxy-1-propanol, 3-phenoxy-1, 2-propanediol, 3-phenoxy-1, 3-propanediol, toluene propanol (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 compounds represented by the following formula (1-1) (hereinafter also referred to as "compound 1").

3- (4- (2-hydroxy-3- (4- (2- (4- (ethylene oxide-2-ylmethoxy) phenyl) propan-2-yl) phenoxy) propoxy) phenyl) propan-2-yl) phenoxy) propane-1, 2-diol … (1-1)

Examples of the alcohol (C) represented by the formula (1) include a compound having a 1-propanol structure formed by opening a terminal epoxy group of a bisphenol F type epoxy resin, a compound having a 1, 2-propanediol structure formed by opening a terminal epoxy group of a bisphenol F type epoxy resin (e.g., bisphenol F glycidyl-2, 3-dihydroxypropyl ether), a compound having a 1-propanol structure formed by opening a terminal epoxy group of a naphthalene type epoxy resin, a compound having a 1, 2-propanediol structure formed by opening a terminal epoxy group of a naphthalene type epoxy resin, a compound having a 1-propanol structure formed by opening a terminal epoxy group of a phenol novolac type epoxy resin, a compound having a 1, 2-propanediol structure formed by opening a terminal epoxy group of a phenol novolac type epoxy resin, a novolac compound having a 1-propanol structure formed by opening a terminal epoxy group of a cresol novolac type epoxy resin, a novolac compound having a 1, 2-propanediol structure formed by opening a terminal epoxy group of a cresol novolac type epoxy resin, and the like.

In particular, from the viewpoint that the effect of lowering the thickening start temperature of the epoxy resin composition of the present embodiment is high and the compatibility with the epoxy resin (a) is good, a uniform epoxy resin composition can be obtained, and the alcohol (C) is preferably 3-phenoxy-1-propanol, 3-phenoxy-1, 2-propanediol, bisphenol a (3-hydroxypropyl) glycidyl ether, bisphenol a (2, 3-dihydroxypropyl) glycidyl ether, or the aforementioned compound 1.

The content of the alcohol (C) in the epoxy resin composition of the present embodiment is not particularly limited, and is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, still more preferably 0.01 parts by mass or more, and still more preferably 0.1 parts by mass or more, based on 100 parts by mass of the total of the epoxy resin (a) and the latent curing agent (B), from the viewpoint of improving the reactivity, as appropriate, depending on the desired performance.

From the viewpoints of stability and physical properties after curing, the amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.

(other curing agent component)

The epoxy resin composition of the present embodiment may contain, as the curing agent component other than the latent curing agent (B), one or more curing agents selected from the group consisting of phenol curing agents, active ester curing agents, amine curing agents, acid anhydride curing agents and thiol curing agents.

< phenolic curing agent >

The phenolic resin curing agent is not particularly limited as long as it can cure the epoxy resin (a), and examples thereof include phenol novolac, bisphenol a novolac, cresol novolac, naphthol novolac, and triazine ring-containing phenol novolac.

From the viewpoint of improving the dielectric loss tangent of the epoxy resin composition of the present embodiment, a phenol novolac containing a triazine ring is preferable as the phenol curing agent. Specifically, LA3018-50P, EXB9808, EXB9829 (manufactured by DIC Co.) and the like are exemplified.

< active ester curing agent >

The active ester curing agent is not particularly limited as long as it functions as a curing agent for the epoxy resin (a) and has an active ester, and is preferably a compound having 2 or more active ester groups in 1 molecule.

From the viewpoint of heat resistance and the like 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 further preferably an active ester compound obtained by reacting a carboxylic acid compound with 1 or 2 or more selected from the group consisting of a phenol compound, a naphthol compound and a thiol compound. Further, it is more preferable that the aromatic compound has 2 or more active ester groups in 1 molecule, which is obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group. Further, it is more preferable that the aromatic compound is obtained by reacting a compound having at least 2 carboxylic acids in 1 molecule with an aromatic compound having a phenolic hydroxyl group, and the aromatic compound has at least 2 active ester groups in 1 molecule.

The active ester curing agent may be linear or branched. In addition, when the "compound having at least 2 carboxylic acids in the 1 molecule" is a compound containing an aliphatic chain, the compatibility of the epoxy resin (a) with the active ester curing agent obtained by using the "compound having at least 2 carboxylic acids in the 1 molecule" is improved. In addition, if the active ester curing agent is a compound having an aromatic ring, the heat resistance of the epoxy resin composition of the present embodiment can be improved.

The carboxylic acid compound used for producing the active ester curing agent is not limited to the following, and examples thereof include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. In particular, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable from the viewpoint of heat resistance of the epoxy resin composition of the present embodiment, and isophthalic acid and terephthalic acid are more preferable.

The thiocarboxylic acid compound used to form the active ester curing agent is not limited to the following, and examples thereof include thioacetic acid and thiobenzoic acid.

Examples of the phenol compound or naphthol compound used for producing the active ester curing agent include, but are not limited to, hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, dicyclopentadiene diphenol, phenol novolac, and the like. Among these, bisphenol a, bisphenol F, bisphenol S, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, dicyclopentadiene diphenol, phenol novolak, more preferably catechol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, dicyclopentadiene diphenol, phenol novolak, still more preferably 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dihydroxybenzophenone, more preferably dihydroxybenzophenone, bisphenol novolak, still more preferably dihydroxybenzophenone, and still more preferably dihydroxyphenol novolak.

The thiol compound used for producing the active ester curing agent is not limited to the following, and examples thereof include benzenedithiol and triazinyl dithiol.

As the active ester curing agent, an active ester compound disclosed in Japanese patent application laid-open No. 2004-277460 may be used, and a commercially available product may be used. The commercially available active ester compound is not limited to the following, but is preferably, for example, a compound containing a dicyclopentadiene diphenol structure, an acetyl compound of a phenol novolac, a benzoyl compound of a phenol novolac, and particularly preferably, a compound containing a dicyclopentadiene diphenol structure. Examples of the compound containing a dicyclopentadiene diphenol structure include EXB9451, EXB9460, and EXB9460S (manufactured by DIC corporation); DC808 (mitsubishi chemical company, inc.) as an acetyl compound of phenol novolac; and YLH1026 (manufactured by Mitsubishi chemical corporation) as a benzoyl compound of phenol novolac.

< amine-based curing agent >

The amine-based curing agent is not limited to the following, and examples thereof include dicyandiamide derivatives such as dicyandiamide, dicyandiamide-aniline adducts, dicyandiamide-methylaniline adducts, dicyandiamide-diaminodiphenylmethane adducts, dicyandiamide-diaminodiphenylether adducts, and the like; guanidine salts such as guanidine nitrate, guanidine carbonate, guanidine phosphate, guanidine sulfamate, and guanidine aminobicarbonate; acetylguanidine, diacetylguanidine, propionylguanidine, dipropionylguanidine, cyanoacetylguanidine, guanidine succinate, diethyl cyanoacetylguanidine, guanylurea, N-oxymethyl-N ' -cyanoguanidine, N ' -dicarbonylethoxyguanidine, metaphenylene diamine, p-phenylenediamine, 3' -diaminodiphenyl sulfone, 4' -diaminodiphenyl methane, 4' -diaminodiphenyl ether, and the like.

When the latent curing agent (B) is an amine curing agent having an amine moiety, it is possible to distinguish whether or not the latent curing agent (B) and the amine curing agent other than the component (B) have a latent property.

< acid anhydride-based curing agent >

The acid anhydride-based curing agent is not limited to the following, and examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

< thiol-based curing agent >

Examples of the thiol curing agent include 3,3' -dithiodipropionic acid, trimethylolpropane tris (mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), ethylene glycol dimercaptoacetate, 1, 4-bis (3-mercaptobutyryloxy) butane, tris [ (3-mercaptopropionyloxy) -ethyl ] -isocyanurate, 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptopropionate), 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril, 4-butanedithiol, 1, 6-hexanedithiol, 1, 10-decanedithiol, and the like, as long as the thiol curing agent contains 2 or more thiol groups in 1 molecule. From the viewpoint of impact resistance of a cured product obtained from the epoxy resin composition of the present embodiment, 1, 4-bis (3-mercaptobutyryloxy) butane, 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1 h,3h,5 h) -trione, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) are preferable, and pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are more preferable from the viewpoint of low-temperature curability of the epoxy resin composition of the present embodiment.

The content of the curing agent component other than the latent curing agent (B) in the epoxy resin composition of the present embodiment is not particularly limited, and is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and even more preferably 1.0 mass% or more, from the viewpoint of reactivity, and may be appropriately set according to the desired properties. From the viewpoint of stability, it is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less.

(film-forming Polymer (D))

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

As the film-forming polymer (D), all polymers having the following functions can be used: when the film is formed by casting or by coating and drying at a predetermined thickness, the occurrence of cracks and fissures can be prevented, and the film shape can be maintained.

The film-forming polymer (D) is not limited to the following, and examples thereof include phenoxy resin, polyvinyl butyral resin, and polyvinyl acetal resin; and elastomers having functional groups such as carboxyl, hydroxyl, vinyl, and amino groups.

The film-forming polymer (D) may be used alone or in combination of 1 or more than 2 kinds.

The film-forming polymer (D) is preferably a phenoxy resin excellent in long-term connection reliability. The phenoxy resin is not limited to the following, and examples thereof include 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, phenoxy resin containing fluorene ring, caprolactone modified bisphenol a type phenoxy resin, and the like.

The molecular weight of the film-forming polymer (D) is not particularly limited, and the number average molecular weight is preferably 9,000 or more and 23,000 or less, more preferably 9,500 or more and 21,000 or less, and still more preferably 10,000 or more and 20,000 or less. The number average molecular weight herein is a number average molecular weight in terms of polystyrene based on gel permeation chromatography (hereinafter referred to as GPC), and is a value obtained by calculating an average value for a region having a molecular weight in terms of polystyrene of 728 or more.

By setting the number average molecular weight of the film-forming polymer (D) to 9,000 or more, the film-forming polymer (D) can be suppressed from penetrating through the crosslinked structure of the cured epoxy resin (a), and the decrease in cohesive force of the cured product of the epoxy resin composition of the present embodiment can be suppressed, and thus, the decrease in connection reliability between substrates in a printed circuit board and between the printed circuit board and a semiconductor package can be suppressed, which is preferable.

On the other hand, the adhesive film obtained by using the epoxy resin composition of the present embodiment as a material for the adhesive layer can maintain high adhesion to an adherend such as a predetermined substrate or IC chip by setting the number average molecular weight of the film-forming polymer (D) to 23,000 or less, and can suppress occurrence of partial curing failure at the time of connection, corrosion of wiring and electrodes is less likely to occur, and high insulation reliability can be obtained, so that it is preferable.

The content of the film-forming polymer (D) in the epoxy resin composition of the present embodiment is not particularly limited, and is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of preventing cracking after the epoxy resin composition of the present embodiment is formed into a film, although the content is appropriately set according to the desired performance. From the viewpoints of the handleability of the varnish and the ease of producing the film, the content is preferably 90 mass% or less, more preferably 80 mass% or less, and still more preferably 70 mass% or less.

By setting the content of the film-forming polymer (D) to the above numerical range, an epoxy resin composition having good storage stability and excellent landfill property and curing property when a film is produced is obtained.

(filler (E))

The epoxy resin composition of the present embodiment preferably further contains a filler (E).

The filler (E) is not particularly limited, and examples thereof include an inorganic filler and an inorganic filler obtained by treating an inorganic filler with a silane coupling agent from the viewpoints of thermal expansion coefficient and thermal conductivity, and an organic filler from the viewpoints of improving adhesive strength and crack resistance.

The filler (E) may be used alone or in combination of 1 or more than 2. The shape of the filler (E) is not particularly limited, and may be any of irregular shape, spherical shape, and scaly shape, for example.

By adding an inorganic filler to the epoxy resin composition of the present embodiment, the thermal expansion coefficient can be adjusted, and heat resistance and moisture resistance tend to be improved.

Examples of the inorganic filler include, but are not limited to, silicates such as talc, calcined clay, uncalcined clay, mica, and glass; oxides such as oxidized silica including titanium oxide, aluminum oxide (corundum), fused silica (fused spherical silica, fused broken silica), synthetic silica, and crystalline silica; carbonates such as calcium carbonate, magnesium carbonate, hydrotalcite, etc.; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates such as barium sulfate and calcium sulfate; sulfite such as calcium sulfite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, and the like; nitride such as aluminum nitride, boron nitride, and silicon nitride. Among these, from the viewpoint of improving heat resistance, moisture resistance and strength of a cured product obtained from the epoxy resin composition of the present embodiment, fused silica, crystalline silica and synthetic silica powder are preferable, and any of silicon oxide, aluminum oxide and boron nitride is preferable. By using these, the thermal expansion coefficient of the cured product obtained from the epoxy resin composition of the present embodiment can be suppressed, and thus improvement in the cold and hot cycle test and the like can be predicted.

When the inorganic filler is used as the filler (E), the content of the inorganic filler in the epoxy resin composition of the present embodiment is not particularly limited, and is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 85% by mass or less, based on the total amount of the epoxy resin composition, although the content is not particularly limited.

When the content of the inorganic filler is 10 mass% or more, an excellent low thermal expansion coefficient tends to be achieved. When the content of the inorganic filler is 90 mass% or less, the increase in elastic modulus tends to be further suppressed.

The inorganic filler is preferably surface-treated with a silane coupling agent.

The performance of the epoxy resin composition of the present embodiment can be exhibited by incorporating a silane coupling agent into the epoxy resin composition, and the epoxy resin composition of the present embodiment tends to be further reduced in viscosity by surface-treating the inorganic filler with the silane coupling agent.

The silane coupling agent is not limited to the following materials, and examples thereof include silane coupling agents such as 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-gamma-aminopropyl trimethoxysilane, N- (2-aminoethyl) 3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyl methyltrimethoxysilane, 3-aminopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyl trimethoxysilane hydrochloride, 3-methacryloxypropyl trimethoxysilane, 3-chloropropylmethyldimethoxysilane, and 3-chloropropyltrimethoxysilane.

Among these, from the viewpoint of the adhesive strength of the epoxy resin composition after curing of the present embodiment, a silane coupling agent having a polymerizable functional group is preferable.

The organic filler has a function as an impact-resistant relaxing agent having stress relaxation property in the epoxy resin composition of the present embodiment.

The epoxy resin composition of the present embodiment further improves the adhesion to various connecting members by containing the organic filler. In addition, the occurrence and the progress of cracks tend to be suppressed.

Examples of the organic filler include, but are not limited to, acrylic resins, silicone resins, butadiene rubbers, polyesters, polyurethanes, polyvinyl butyrals, polyarylates, polymethyl methacrylates, acrylic rubbers, polystyrene, NBR, SBR, silicone-modified resins, and organic fine particles of copolymers containing these as components.

From the viewpoint of improving the adhesion, the organic fine particles are preferably, for example, alkyl (meth) acrylate-butadiene-styrene copolymer, alkyl (meth) acrylate-silicone copolymer, silicone- (meth) acrylic copolymer, a complex of silicone and (meth) acrylic acid, a complex of alkyl (meth) acrylate-butadiene-styrene and silicone, and a complex of alkyl (meth) acrylate and silicone.

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

Examples of the core-shell type organic fine particles include, but are not limited to, particles obtained by grafting an acrylic resin onto an acrylic copolymer, and particles obtained by grafting an acrylic resin onto a silicone-acrylic rubber.

By realizing low elastic modulus by containing core-shell organic fine particles, stress generated in the chamfer portion is reduced, and crack generation tends to be suppressed. In addition, when cracks occur, the core-shell organic fine particles contained therein function as a stress relaxation agent, and tend to suppress the progress of cracks.

As a constituent material of the core layer, a material excellent in flexibility is preferably used. The constituent material of the core layer is not limited to the following, and examples thereof include silicone-based elastomers, butadiene-based elastomers, styrene-based elastomers, acrylic-based elastomers, polyolefin-based elastomers, and silicone/acrylic composite-based elastomers.

On the other hand, as a constituent material of the shell layer, a material excellent in affinity for other components of the semiconductor resin sealing material, in particular, for the epoxy resin is preferable. The material constituting the shell layer is not limited to the following, and examples thereof include an acrylic resin, an epoxy resin, and the like. Among these, acrylic resins are particularly preferred from the viewpoints of affinity for other components in the epoxy resin composition of the present embodiment, particularly for the epoxy resin (a).

When the organic filler is used as the filler (E), the content of the organic filler in the epoxy resin composition of the present embodiment is not particularly limited, and is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 18% by mass or less, and still more preferably 3% by mass or more and 16% by mass or less, based on the total amount of the epoxy resin composition, although the content is not particularly limited.

When the content of the organic filler is 1 mass% or more, the effect of improving the adhesive strength of the epoxy resin composition of the present embodiment, which exerts the effect of stress relaxation, can be obtained. The effect of improving the reflow resistance of the epoxy resin composition of the present embodiment can be obtained by setting the content of the organic filler to 20 mass% or less.

(additive (F))

The epoxy resin composition of the present embodiment may further contain other additives (F) than the above-mentioned alcohol (C), film-forming polymer (D) and filler (E).

As the additive (F), for example, a reactive diluent, a solvent, a thermoplastic polymer, a stabilizer, a liquid low-stress agent, a flame retardant, a leveling agent, and the like can be used from the viewpoint of adjusting the viscosity of the epoxy resin composition of the present embodiment.

The additive (F) may be used alone or in combination of 1 or more than 2.

The content of the additive (F) is not particularly limited, and is preferably 0.00001 mass% or more, more preferably 0.0001 mass% or more, and still more preferably 0.001 mass% or more, based on the entire epoxy resin composition of the present embodiment, although the content is appropriately set according to the desired performance. The content of the additive (F) is preferably less than 20 mass%, more preferably less than 15 mass%, still more preferably less than 10 mass%, still more preferably less than 8 mass%, still more preferably less than 7 mass%, particularly preferably less than 6 mass%, still more preferably less than 5 mass%, particularly preferably less than 3 mass%, and particularly preferably less than 2 mass% relative to the entire epoxy resin composition of the present embodiment.

< reactive diluent >

The reactive diluent can react with the latent curing agent (B) to form a part of the cured product while reducing the viscosity of the epoxy resin composition of the present embodiment.

As the reactive diluent, a compound having 1 or more glycidyl groups in its molecule can be used. The reactive diluent is not limited to the following, and examples thereof include butyl glycidyl ether, diglycidyl aniline, N' -glycidyl-o-toluidine, phenyl glycidyl ether, ethylene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1, 6-hexanediol diglycidyl ether.

Further, epoxy resins that can be used as the reactive diluents are exemplified. That is, examples of the reaction diluent include glycidyl amine type epoxy resins such as 2-ethylhexyl glycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol a type epoxy resins, silicone modified epoxy resins, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentadiene type diglycidyl ether, trimethylolpropane triglycidyl ether, vinyl (3, 4-cyclohexene) dioxide, 2- (3, 4-epoxycyclohexyl) -5, 1-spiro- (3, 4-epoxycyclohexyl) -m-dioxane, tetraglycidyl bis (aminomethyl) cyclohexane; various epoxy resins such as 1, 3-diglycidyl-5-methyl-5-ethylhydantoin type epoxy resin, 1, 3-bis (3-glycidoxypropyl) -1, 3-tetramethyldisiloxane type epoxy resin, phenyl glycidyl ether, tolyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, N-glycidyl phthalimide, N-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, α -pinene oxide, allyl glycidyl ether, 1-vinyl-3, 4-epoxycyclohexane, 1, 2-epoxy-4- (2-methyl oxiranyl) -1-methylcyclohexane, 1, 3-bis (3-glycidoxypropyl) -1, 3-tetramethyldisiloxane, and neodecanoic acid glycidyl ester.

Various monoepoxy compounds and glycidyl ether compounds of a polyol may be used as the reactive diluent, and they have only 1 functional group (epoxy group or glycidyl group) contributing to the reaction with the latent curing agent (B) in 1 molecule, and thus three-dimensional crosslinking cannot be formed at the time of curing, and therefore, the glass transition temperature (Tg) and toughness of the cured product of the epoxy resin composition of the present embodiment tend to be insufficient. Thus, a compound containing 2 or more glycidyl groups in 1 molecule as a reactive diluent is preferable because it can form three-dimensional crosslinks upon curing. Thus, the glass transition temperature (Tg) and toughness at the time of curing tend to be suppressed from decreasing.

The reactive diluent may be used alone or in combination of 1 or more than 2.

The content of the reactive diluent in the epoxy resin composition of the present embodiment is not particularly limited, and is preferably 1.0 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the epoxy resin (a), although the content is appropriately set according to the desired performance. The content of the reactive diluent is set to 1.0 part by mass or more, whereby the following tends to be present: when the epoxy resin composition of the present embodiment is used as a wiring landfill film, excellent landfill properties can be obtained while suppressing an increase in viscosity of the epoxy resin composition at normal temperature. In addition, there is a tendency that: the epoxy resin composition of the present embodiment is suppressed in lowering of the glass transition temperature (Tg) and toughness at the time of curing, and in occurrence and progression of chamfer cracks.

On the other hand, the content of the reactive diluent tends to be 30 parts by mass or less with respect to 100 parts by mass of the epoxy resin (a), as follows: inhibit the decrease of adhesion with the adherend and inhibit the peeling in the moisture absorption reflow test.

In addition, the content of the reactive diluent can be adjusted to be large in order to suppress the increase in viscosity of the epoxy resin composition that occurs when the filler (E) is highly filled.

< solvent >

The solvent is not limited to the following, and examples thereof include halogen solvents such as methylene chloride and chloroform; aromatic solvents such as benzene, toluene, xylene, and mesitylene; aliphatic ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone; ketone solvents such as aromatic ketones such as acetophenone, etc.

In addition, a solvent such as ethyl acetate, dimethylformamide, methyl cellosolve, propylene glycol monomethyl ether, or the like may be used in combination with the above solvents. Among these, ethyl acetate is preferably used as the ester from the viewpoints of solubility and boiling point of the epoxy resin composition of the present embodiment.

As the solvent to be combined with ethyl acetate, an aromatic solvent having a boiling point of 120℃or lower such as toluene is preferable. The solvent may be used alone or in combination of 1 or more than 2.

< thermoplastic Polymer >

The thermoplastic polymer is not limited to the following, and examples thereof include polyamide resins, polyimides, polyester resins, polyurethane resins, acrylic resins, vinyl carboxylates, polyether resins, and the like. Among these, acrylic resins are preferable, and vinyl carboxylates are more preferable. The thermoplastic polymer may be used alone or in combination of 1 or more than 2 kinds.

The acrylic resin is preferably an acrylic resin having a glass transition temperature (Tg) of 25 ℃ or less, more preferably 1 or more selected from the group consisting of a hydroxyl group-containing acrylic resin, a carboxyl group-containing acrylic resin, an anhydride group-containing acrylic resin, an epoxy group-containing acrylic resin, an isocyanate group-containing acrylic resin, and a urethane group-containing acrylic resin, and still more preferably a phenolic hydroxyl group-containing acrylic resin. Here, the "acrylic resin" refers to a resin containing a (meth) acrylate structure, and in these resins, the (meth) acrylate structure may be contained in the main chain or in the side chain.

The number average molecular weight (Mn) of the acrylic resin is preferably 10,000 or more and 1,000,000 or less, more preferably 30,000 or more and 900,000 or less. Here, the number average molecular weight (Mn) of the acrylic resin is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

The functional group equivalent in the case where the acrylic resin has a functional group is preferably 1000 or more and 50000 or less, more preferably 2500 or more and 30000 or less.

The vinyl carboxylate may contain a monomer copolymerizable with the aforementioned vinyl carboxylate as a monomer unit. Examples of such monomers include allyl carboxylates, alkyl (meth) acrylates, and specifically allyl acetate, methyl (meth) acrylate, and ethyl (meth) acrylate.

< stabilizer >

The stabilizer may be a material that improves storage stability, and examples thereof include boric acid and cyclic borate compounds.

The cyclic borate compound means a compound containing boron in a cyclic structure. The cyclic borate compound is preferably 2,2 '-oxybis (5, 5' -dimethyl-1, 3, 2-dioxaborane).

The stabilizer may be used alone or in combination of 1 or more than 2.

< liquid Low stress agent >

The liquid low-stress agent is not limited to the following, and examples thereof include polyalkylene glycols and amine-modified products thereof, polybutadiene, acrylonitrile, and other organic rubbers; silicone rubber such as dimethylsiloxane; silicone oil, etc.

The liquid low-stress agent may be used alone or in combination of 1 or more than 2.

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, more preferably 10 parts by mass or more and 20 parts by mass or less, relative to the mass (100 parts by mass) of the epoxy resin (a).

< flame retardant >

The flame retardant is not limited to the following, and examples thereof include brominated flame retardants, phosphorus flame retardants, and inorganic flame retardants.

The brominated flame retardant is not limited to the following, and examples thereof include tetrabromophenol.

The phosphorus flame retardant is not limited to the following, and examples thereof include 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and its epoxy derivative, triphenylphosphine or its derivative, phosphate, condensed phosphate, phosphazene compound, and the like.

The nitrogen-based flame retardant is not limited to the following, and examples thereof include guanidine-based flame retardants, phenols having a triazine structure, melamine polyphosphates, and isocyanuric acid.

The inorganic flame retardant compound is not limited to the following, and examples thereof include magnesium hydroxide and aluminum hydroxide. From the viewpoint of heat resistance, the inorganic flame retardant compound is preferably magnesium hydroxide.

The flame retardant may be used alone or in combination of 1 or more than 2.

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, more preferably 10 parts by mass or more and 100 parts by mass or less, based on the mass (100 parts by mass) of the epoxy resin (a).

< leveling agent >

The leveling agent is not limited to the following, and examples thereof include silicone leveling agents and acrylic leveling agents.

The leveling agent may be used alone or in combination of 1 or more than 2 kinds.

[ adhesive film ]

The adhesive film of the present embodiment has a support, and a resin layer containing the epoxy resin composition of the present embodiment is provided on the support.

The support is not limited to the following, and examples thereof include polyolefin such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter, sometimes abbreviated as "PET"), and polyethylene naphthalate; polycarbonates, polyimides; further, a release paper, a copper foil, a metal foil such as an aluminum foil, or the like may be subjected to a release treatment in addition to the matting treatment and the corona treatment. The thickness of the support is preferably 10 μm or more and 150 μm or less.

From the viewpoint of reliability, the resin layer preferably contains 50 mass% or more and 100 mass% or less of the epoxy resin composition of the present embodiment. The resin layer may additionally contain conductive particles.

The adhesive film according to the present embodiment can be used as an adhesive film for forming a laminate layer of a printed wiring board and an adhesive film for insulating layers of a semiconductor chip package.

The printed circuit board of the present embodiment includes the cured product of the adhesive film, and the semiconductor chip package of the present embodiment includes the cured product of the adhesive film.

The semiconductor device of the present embodiment includes the printed circuit board and/or the semiconductor chip package.

[ method for producing epoxy resin composition ]

The epoxy resin composition of the present embodiment can be produced by mixing the epoxy resin (a), the latent curing agent (B), and if necessary, a curing agent other than the latent curing agent (B), the alcohol (C), the film-forming polymer (D), the filler (E), the additive (F), and the like. Methods well known in the art can be applied to the mixing method. Examples of the method include a method of heating and mixing the resin compositions to a temperature at which curing does not occur, and a method of dissolving or dispersing each resin composition in an organic solvent or preparing a varnish.

[ method for producing adhesive film ]

As a method for producing the adhesive film, for example, a varnish of an epoxy resin composition is obtained by dissolving or uniformly dispersing an epoxy resin (a), a latent curing agent (B), and, if necessary, a curing agent other than the latent curing agent, an alcohol (C), a film-forming polymer (D), a filler (E), an additive (F), and the like in a solvent by heating, and then cooling to 50 ℃ or less if necessary. The solid content concentration in the varnish is not particularly limited, but is preferably 30 mass% or more and 80 mass% or less.

The solvent is not limited to the following, and examples thereof include halogen solvents such as methylene chloride and chloroform; aromatic solvents such as benzene, toluene, xylene, and mesitylene; aliphatic ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone; ketone solvents such as aromatic ketones such as acetophenone, etc. In addition, other solvents such as ethyl acetate, dimethylformamide, methyl cellosolve, propylene glycol monomethyl ether, and the like may be used in combination. Among these, ethyl acetate is preferably used in combination as the other solvent from the viewpoint of solubility and boiling point of the epoxy resin composition. As the solvent to be combined with ethyl acetate, an aromatic solvent having a boiling point of 120℃or lower such as toluene is preferably used. The solvent may be used alone or in combination of 1 or more than 2.

In the step of producing the adhesive film according to the present embodiment, the epoxy resin composition according to the present embodiment is preferably dissolved in a mixed solvent containing ethyl acetate at room temperature. Reference herein to dissolution occurring at room temperature means: when mixed at a solid content concentration of 10 mass%, a solution state can be obtained at room temperature, which means a state in which a solid content is substantially absent and can be maintained for 1 day or more, preferably 30 days or more.

The adhesive film of the present embodiment can be produced by applying the varnish of the epoxy resin composition to a support film, and then heating and drying the support film to remove the solvent and to produce a film. Thus, a semi-cured adhesive film can be obtained. The thickness of the adhesive film after the heat drying is preferably 5 μm or more and 200 μm or less, more preferably 5 μm or more and 120 μm or less, still more preferably 7 μm or more and 70 μm or less, still more preferably 10 μm or more and 20 μm or less.

The thickness of the adhesive film of the present embodiment is preferably 200 μm or less from the viewpoint of enabling reduction of the number of components used. More preferably 120 μm or less, still more preferably 70 μm or less, still more preferably 20 μm or less. In addition, from the viewpoint of securing landfill property and insulation property, the thickness is preferably 5 μm or more. More preferably 7 μm or more, and still more preferably 10 μm or more.

The heating and drying conditions are those in which the heating temperature is 60 ℃ to 150 ℃, preferably 90 ℃ to 120 ℃, and the heating time is 1 minute to 20 minutes, preferably 2 minutes to 10 minutes.

When the heating and drying conditions are within this range, the solvent remaining in the obtained adhesive film is sufficiently removed, and the volatile component in the adhesive film can be made to be 1 mass% or less. Further, curing of the adhesive film due to film formation can be suppressed, and thus, when the adhesive film according to the present embodiment is used by being laminated on a predetermined inner layer circuit board, landfill property between wirings can be ensured.

In the step of producing the adhesive film, a known method may be applied as a method of applying the varnish containing the epoxy resin composition of the present embodiment to the support, and examples thereof include, but are not particularly limited to, bar coater, lip coater, die coater, roll coater, blade coater, and the like.

[ printed Circuit Board ]

The printed wiring board of the present embodiment includes a layer obtained by curing the adhesive film of the present embodiment. In the case of manufacturing a printed wiring board using an adhesive film, the adhesive film manufactured by the above method is adhered to a patterned inner layer circuit board, and laminated while being pressed and heated from the support side. The inner circuit surface may be roughened in advance. Lamination is carried out under atmospheric or reduced pressure by batch or roll-based continuous, preferably simultaneous lamination on both sides. The lamination conditions at this time are preferably: the pressure welding temperature is 70-150 ℃ and the pressure welding pressure is 0.1-60 MPa. In addition, from the viewpoint of reducing voids, lamination is preferably performed under reduced pressure of 2KPa or less. The pressure of the pressure is preferably 40MPa or less from the viewpoint of maintaining the thickness of the adhesive film after the pressure bonding.

After lamination, the support is peeled off from the adhesive film after cooling to room temperature, and then the resin layer laminated on the inner circuit board is heat-cured. As the curing conditions, preferred are: the curing temperature is 130-250 ℃ and the curing time is 30-180 minutes.

Next, after forming a portion to be a through hole by a laser such as a carbon dioxide laser, roughening treatment is performed by using an oxidizing agent such as permanganate, dichromate, or ozone for the purpose of removing dirt and improving adhesion to a plating layer. Thereafter, a conductor circuit is selectively formed on the resin layer of the edge layer by electroless plating or electrolytic plating, and simultaneously a conductor layer is formed on the inner wall of the through hole, thereby forming an outer layer circuit. Thereafter, the conductive layer and the resin layer are annealed at a temperature in the range of 150 to 250 ℃ for a time in the range of 30 to 60 minutes, whereby the adhesion between the conductive layer and the resin layer can be improved. Further, the adhesive film according to the present embodiment is used for the conductor circuit layer obtained in this manner, and the above-described production method is repeated, whereby a multi-stage laminate layer can be formed to produce a multi-layer printed circuit board.

In the heat curing, it is preferable to carry out the curing under the condition of 220℃or lower from the viewpoint of volatilizing the organic compound and suppressing decomposition.

[ semiconductor chip Package, semiconductor device ]

The semiconductor chip package of the present embodiment includes the cured product of the adhesive film.

The semiconductor device of the present embodiment includes the printed circuit board and/or the semiconductor chip package.

[ method of Using adhesive film ]

Preferably, it is: the adhesive film of the present embodiment is laminated under a pressure of 40MPa or less as described in the above [ printed circuit board ], and then heat-cured under a heating condition of 220 ℃ or less to produce a predetermined laminate and a semiconductor chip package.

The pressure is more preferably 20MPa or less, and still more preferably 10MPa or less.

The temperature of the heat curing is more preferably 200℃or lower, and still more preferably 180℃or lower.

By setting the pressure of the pressure to 40MPa or less, a practically sufficient thickness can be ensured after the pressure is applied.

In addition, by setting the temperature of the heat curing to 220 ℃ or lower, the organic compound can be sufficiently volatilized, and further, decomposition of the resin layer of the adhesive film can be prevented.

Examples

Hereinafter, the present embodiment will be described in more detail by way of examples and comparative examples, which are given as illustrative descriptions, and the present invention is not limited to the examples and comparative examples. That is, those skilled in the art can apply various modifications to the embodiments shown below to implement the present invention.

The "parts" are mass references unless otherwise specified.

The values of various production conditions and evaluation results in the following examples have meanings as preferable values of the upper limit or the lower limit in the embodiment of the present invention. The preferable range has a meaning of a preferable value as the above-described upper limit or lower limit, and the preferable range may be a range defined according to a combination of the value of the above-described upper limit or lower limit and the value of the below-described embodiment or the values of each other.

[ production of constituent Material of epoxy resin composition ]

Hereinafter, examples of production of constituent materials used in the epoxy resin compositions of examples and comparative examples described below are shown.

(production example 1) production of curing agent 1 for epoxy resin

Bisphenol A type epoxy resin (trade name "jER828EL" manufactured by Mitsubishi chemical corporation) 1 equivalent and 2-ethyl-4-methylimidazole 1 equivalent (in terms of active hydrogen) were reacted in a 1:1 mixed solvent of n-butanol and toluene at 80 ℃. Thereafter, the excess amine was distilled off together with the solvent under reduced pressure, and a solid block-shaped curing agent for epoxy resins was obtained at 25 ℃.

Next, the bulk epoxy resin curing agent was pulverized by a jet mill, and classification was carried out by a classifier to obtain a specific surface area value of 3.63m ² The epoxy resin curing agent 1 is a curing agent for epoxy resin having an undersize average particle diameter D50 of 2.50 μm and a D99/D50 of 5.4.

(production example 2) production of curing agent 2 for encapsulated epoxy resin

100 parts by mass of the aforementioned curing agent 1 for epoxy resin was uniformly dispersed in 200 parts by mass of hexane, and 30 parts by mass of an encapsulating agent (trade name "MR-400" manufactured by Tosoh Co., ltd.) was added thereto, and the mixture was stirred at 50℃for 3 hours to obtain an encapsulated curing agent 2 for epoxy resin which was solid at 25 ℃.

As a result of IR measurement of the obtained curing agent 2 for epoxy resin, it was confirmed in the shell that the wave number originated from 1630cm was a result of absorption ^-1 Above and 1680cm ^-1 The following infrared-ray-bonded group (x) originated from the absorption wavenumber 1680cm ^-1 Above and 1725cm ^-1 The following infrared bonding group (y) originated from absorption wave number 1730cm ^-1 Above 1755cm ^-1 The following peak of the infrared bonding group (z).

(production example 3) production of curing agent 3 for epoxy resin

The curing agent 1 for epoxy resin obtained in the above-mentioned (production example 1) was used, and KRYPTRON-ORB manufactured by EARTHTECHNICA was used under the conditions of a temperature of 10℃and a humidity of 30%, a rotation speed of 13500rpm, a supply speed of 10kg/hr and an air volume of 3m ³ And (3) performing shape correction treatment under the condition of/min. The classifier was equipped with a cyclone collector and a bag filter, and classification was carried out to obtain a specific surface area of 2.67m ² The curing agent 3 for epoxy resin, which is a curing agent for epoxy resin having a D99/D50 of 3.1 μm and a particle size distribution of 4.5.

(production example 4) production of curing agent 4 for encapsulated epoxy resin

100 parts by mass of the aforementioned curing agent 3 for epoxy resin was uniformly dispersed in 200 parts by mass of hexane, and 20 parts by mass of an encapsulating agent (trade name "CORONATE T100" manufactured by Tosoh Co., ltd.) was added thereto, and the reaction was continued for 3 hours while stirring at 50℃to obtain an encapsulated curing agent 4 for epoxy resin, which was solid at 25 ℃.

As a result of IR measurement of the obtained curing agent 4 for epoxy resin, it was confirmed in the shell that the wave number originated from 1630cm was a result of absorption ^-1 Above and 1680cm ^-1 The following infrared-ray-bonded group (x) originated from the absorption wavenumber 1680cm ^-1 Above and 1725cm ^-1 The following infrared bonding group (y) originated from absorption wave number 1730cm ^-1 Above 1755cm ^-1 The following peak of the infrared bonding group (z).

(production example 5) production of curing agent 5 for epoxy resin

1 equivalent of bisphenol A type epoxy resin (trade name "jER828EL" manufactured by Mitsubishi chemical corporation) and 1 equivalent of 2-methylimidazole (in terms of active hydrogen) were reacted in a 1:1 mixed solvent of n-butanol and toluene at 80 ℃. Thereafter, the excess imidazole was distilled off together with the solvent under reduced pressure to obtain a block-shaped curing agent for epoxy resins which was solid at 25 ℃. Pulverizing the obtained curing agent for epoxy resin by using a turbine mill to obtain a specific surface area value of 0.36m ² And/g, the undersize average particle diameter D50 was 9.80. Mu.m, and the D99/D50 was 4.2.

(production example 6) production of Polymer D-1 for film formation

170 parts by mass of a biphenyl type epoxy resin (trade name "YX4000" manufactured by Mitsubishi chemical corporation) and biphenol: 110 parts by mass of xylene: 30 parts by mass and triethylamine: 0.05 parts by mass of a catalyst was mixed and reacted at 170℃for 2 hours while stirring under a nitrogen atmosphere. After the completion of the reaction, it took 3 hours to raise the temperature to 200℃while removing xylene from the system, and the reaction was continued at 200℃for 7 hours to obtain a film-forming polymer D-1 having a number average molecular weight of 22,500.

Production of alcohol C-1 (production example 7)

Bisphenol A diglycidyl ether (BADGE, aldrich reagent, epoxy equivalent 172 g/eq): 50 parts by mass of methanol: 10 parts by mass of water: 1 part by mass and trimethyl ammonium chloride: 0.005 parts by mass was mixed and the reaction was carried out at 60℃for 2 hours under nitrogen atmosphere with stirring.

After the completion of the reaction, methanol and residual water were distilled off at 140℃under reduced pressure to give alcohol C-1 having an alcoholic hydroxyl equivalent of about 20000 g/eq.

[ method of evaluating Properties ]

Hereinafter, the evaluation methods of the characteristics of the resin compositions of examples and comparative examples described below are shown.

(1) evaluation of film storage stability

A50% MEK (methyl ethyl ketone) solution of the epoxy resin compositions of examples and comparative examples was prepared to prepare varnishes. Immediately after the varnish was prepared, the resultant was coated on a PET film to a thickness of about 50 μm using a coater, and then dried in an oven at 100 ℃ for 5 minutes to obtain an adhesive film.

FT-IR measurement was performed on the obtained adhesive film, and 926cm derived from an epoxy group was calculated ^-1 Peak (P1) of (C) and 1510cm from phenyl ^-1 The peak ratio F1 (P1/P2) of the peak (P2) of (C).

Further, after the adhesive film was stored at 9℃for 30 days, FT-IR was measured by the same method, and the peak ratio F2 (P1/P2) after storage was calculated.

In order to compare the aforementioned F1 with F2, the residual amount of the peak ratio of the epoxy group ((F2/F1). Times.100) was calculated. The peak ratio residual amount of the epoxy group is evaluated as "verygood" if it is 90% or more and 99% or more, as "good" if it is 70% or more and less than 90%, as "delta" if it is 50% or more and less than 70%, and as "x" if it is less than 50%.

(2) evaluation of landfill Property

On an FR-5 substrate (17 cm. Times.34 cm, thickness 0.4 mm) on which wiring lines having a line/space of 10 μm and a wiring thickness of 7 μm were applied, which was drawn by a direct imaging process using a dry film resist, the adhesive film produced in the above (1) was laminated on one side of the substrate with a PET film in a state of having a press bonding temperature of 90℃and a press bonding pressure of 0.3 to 0.5MPa and a lamination speed of 0.4 m/min, using a roll laminator.

The presence of bubbles was visually examined by judging that the gaps between the wirings were free of resin as bubbles, and the cases where no bubbles were present were evaluated as "o", and the cases where bubbles were present were evaluated as "x".

(evaluation of (3) warping Property)

After lamination in the test of the aforementioned (2), the PET film was peeled off from the adhesive film, and further pressure-bonding cured at 175℃for 45 minutes and 40MPa to obtain a test piece. After curing, the test piece was placed in a state of being protruded downward at room temperature, and when one side of 17cm of the test piece was pressed against a table, the height of the other side floating from the table was measured.

At this time, the table was evaluated as "verygood" when the height was less than 1.0cm, was evaluated as "good" when the height was 1.0cm or more and less than 1.5cm, was evaluated as "delta" when the height was 1.5 or more and less than 3cm, and was evaluated as "×" when the height was 3cm or more.

(4) evaluation of Heat resistance

In the test piece produced by the above-mentioned method ((3) warpage), the portion where no bubble was present was cut into a size of 0.5cm×0.5cm, and the test piece was heated at a constant temperature of 288 ℃ using a measuring instrument TMAQ400 (manufactured by TA instruments corporation), and the time until expansion occurred was measured.

The time until the occurrence of swelling was evaluated as "good" when it was not less than 60 minutes, as "delta" when it was not less than 45 minutes and less than 60 minutes, and as "×" when it was not more than 45 minutes.

(5) evaluation of peel Strength

The PET film was peeled off, and the film-like adhesive was sandwiched between an FR-5 substrate and a copper foil having a foil thickness of 1/2 o/z, and was pressure-bonded at 165℃for 30 minutes at 40 MPa. Then, a scratch was made on a portion of the copper foil having a width of 10mm and a length of 150mm, and the 90-degree peel strength was measured.

The peel strength was evaluated as "good" when it was 1.0kgf/cm or more, as "good" when it was 0.8kgf/cm or more and less than 1.0kgf/cm, as "delta" when it was 0.6 or more and less than 0.8, as "×" when it was 0.4 or more and less than 0.6, and as "×" when it was less than 0.4.

(6) determination of dielectric constant and dielectric loss tangent)

The PET film was peeled off, and 40 sheets of the film-like adhesive were stacked, and cured at 180℃under reduced pressure for 60 minutes to obtain a cured product.

The obtained cured product was cut into a width of 2mm and a length of 80mm to obtain test pieces. The test piece was subjected to measurement of dielectric constant (. Epsilon.) and dielectric loss tangent (tan. Delta.) by the cavity resonance method at a measurement frequency of 1.0GHz using a cavity resonator perturbation method dielectric constant measurement device manufactured by Kato applied electronic development Co., ltd.) and a network analyzer E8362B manufactured by Agilent Technologies Co.

The measurement was performed on 5 test pieces, and an average value was calculated, and when the value of ∈×tan δ was less than 0.01, it was evaluated as "excellent" when it was 0.01 or more and less than 0.012, it was evaluated as "delta" when it was 0.012 or more and less than 0.015, and it was evaluated as "×" when it was 0.015 or more.

Examples 1 to 10 and comparative examples 1 and 2

The epoxy resin composition was obtained by dissolving or uniformly dispersing the component (a), the component (B), the component (D), the other curing agent component, the filler (E) and the additive (F) in a solvent heated to 60 ℃ in accordance with the compounding ratio shown in tables 1 and 2, cooling to 30 ℃, and further mixing and uniformly dispersing the component (C).

The epoxy resin composition was applied to a PET film at a thickness of about 50 μm by a die coater, and then dried in an oven at 100 ℃ for 5 minutes, thereby producing an adhesive film for the evaluation.

[ constituent Material of epoxy resin composition ]

The components shown in tables 1 and 2 below are shown below.

((A) epoxy resin)

A-1: EPICLON 850CRP (bisphenol A type epoxy resin, manufactured by DIC Co., ltd., epoxy equivalent weight: 175 g/eq)

A-2: YX4000 (biphenyl type epoxy resin, manufactured by Mitsubishi chemical corporation, having an epoxy equivalent of 170 g/eq)

A-3: NC3000H (biphenyl aralkyl type epoxy resin, manufactured by Japanese chemical Co., ltd., epoxy equivalent weight of 269 g/eq)

A-4: HP4710 (naphthalene type epoxy resin, manufactured by DIC Co., ltd., epoxy equivalent weight of 170 g/eq)

A-5: YX7760 (fluorine-containing epoxy resin, manufactured by Mitsubishi chemical corporation, epoxy equivalent of 235 g/eq)

Component (B)

B-1: curing agent 1 for epoxy resin of production example 1

B-2: curing agent 2 for epoxy resin of production example 2

B-3: curing agent 3 for epoxy resin of production example 3

B-4: curing agent 4 for epoxy resin of production example 4

B-5: curing agent 5 for epoxy resin of production example 5

(other curing agent component)

DMAP: 4-dimethylaminopyridine (moisture content 1.7% and specific surface area 0.1m, manufactured by Guangrong chemical Co., ltd.) ² /g, undersize mean particle diameter D50 of 15.4. Mu.m, D99/D50 of 6.4)

LA7054: (phenol novolak type resin, produced by DIC Co., ltd., hydroxyl equivalent weight of 125 g/eq)

LA3018: (phenol novolak type resin, DIC Co., ltd., hydroxyl equivalent weight: 150 g/eq)

EXB9460S: (active ester resin, DIC Co., ltd., ester equivalent weight was 223 g/eq)

HPC8000: (active ester resin, DIC Co., ltd., ester equivalent weight was 223 g/eq)

((C) component)

C-1: preparation example 7 alcohol

C-2: 3-phenoxy-1-propanol (reagent, tokyo chemical Co., ltd.)

C-3: 3-phenoxy-1, 2-propanediol (reagent, tokyo chemical Co., ltd.)

((D) film-forming Polymer)

D-1: preparation example 6 film-forming Polymer

D-2: YP50 (phenoxy resin (Nitro iron chemical & Material Co.))

((E) component)

E-1: synthesis of spherical silica SO-C2 (manufactured by ADMATECHS Co.) ((F) component) by aminosilane treatment

F-1: YED216L (1, 6-hexanediol diglycidyl ether, mitsubishi chemical Co., ltd.)

F-2: CDMDG (1, 4-cyclohexanedimethanol diglycidyl ether, manufactured by Zhaoand electric company)

TABLE 1

TABLE 2

As shown in tables 1 and 2, in examples 1 to 10, the epoxy resin compositions which were excellent in storage stability after being formed into films, excellent in filling property and curing property of micro wiring, and capable of achieving both storage stability and reactivity were obtained.

The present application is based on japanese patent applications (japanese patent application publication nos. 2020-212769 and 2021, 1, 18) in the japanese patent application at month 12 and 22 in 2020, and the contents thereof are incorporated herein by reference.

Industrial applicability

The epoxy resin composition of the present application is industrially applicable in the fields of adhesive films, printed circuit boards, semiconductor chip packages, semiconductor devices, and the like, in which multilayering, miniaturization and high density of wiring, low dielectric loss tangent, and the like are required.

Claims (22)

1. An epoxy resin composition comprising an epoxy resin (A) and a latent curing agent (B),

the latent hardener (B) is solid at 25 ℃.

2. The epoxy resin composition according to claim 1, further comprising an alcohol (C) represented by the following formula (1),

in the formula (1), R ₁ ～R ₉ Each independently is one selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkyl group, an aromatic group, a substituent containing a hetero atom, and a substituent containing a halogen atom, R ₁ ～R ₉ Are optionally identical or different from one another and are selected from R ₅ ～R ₉ Optionally bonded to each other to form a ring structure, which is optionally a condensed ring with the benzene ring shown in the formula.

3. The epoxy resin composition according to claim 1 or 2, wherein the latent curing agent (B) is an amine-based curing agent having an amine site.

4. The epoxy resin composition according to any one of claims 1 to 3, wherein a particle size D50 of 50% of the undersize cumulative fraction of the latent curing agent (B) exceeds 0.3 μm and is 10 μm or less, and a particle size distribution expressed by a ratio (D99/D50) of a particle size D99 of 99% of the undersize cumulative fraction to the particle size D50 of 50% of the undersize cumulative fraction is 6 or less.

5. The epoxy resin composition according to any one of claims 1 to 4, wherein the latent curing agent (B) has a specific surface area value (=y (m) ² /g)) and the particle diameter D50 (=x (μm)) of the undersize cumulative fraction 50% satisfy the relationship shown by the following formula (2),

4.0X-1≤Y≤8.3X-1 (2)

when the latent curing agent (B) is a latent curing agent obtained by encapsulating a curing agent component with an encapsulating agent, the curing agent component before encapsulation satisfies the above formula (2).

6. The epoxy resin composition according to any one of claims 1 to 5, wherein the latent curing agent (B) has a core (c) as a curing agent component and a shell(s) covering the core (c),

the shell(s) has an absorption wave number of at least 1630cm ^-1 Above and 1680cm ^-1 The following infrared bonding group (x), absorption wavenumber 1680cm ^-1 Above and 1725cm ^-1 The following infrared bonding group (y) and absorption wave number 1730cm ^-1 Above 1755cm ^-1 The following infrared bonding group (z).

7. The epoxy resin composition according to any one of claims 2 to 6, wherein R in the formula (1) ₁ Is hydroxyl.

8. The epoxy resin composition according to any one of claims 2 to 7, wherein the alcohol (C) is contained in an amount of 0.001 to 20 parts by mass based on 100 parts by mass of the total of the epoxy resin (a) and the latent curing agent (B).

9. The epoxy resin composition according to any one of claims 2 to 8, wherein the alcohol (C) is contained in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the total of the epoxy resin (a) and the latent curing agent (B).

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

11. The epoxy resin composition according to any one of claims 1 to 10, further comprising a film-forming polymer (D).

12. The epoxy resin composition according to any one of claims 1 to 11, further comprising a filler (E).

13. The epoxy resin composition according to any one of claims 1 to 12, wherein the filler (E) is an inorganic filler.

14. The epoxy resin composition according to any one of claims 1 to 13, further comprising an additive (F).

15. An adhesive film comprising a support and, on the support, a resin layer comprising the epoxy resin composition according to any one of claims 1 to 14.

16. The adhesive film according to claim 15, which has a thickness of 20 μm or less.

17. The adhesive film according to claim 15 or 16, which is an adhesive film for forming a laminate layer of a printed circuit board.

18. The adhesive film according to claim 15 or 16, which is an adhesive film for an insulating layer of a semiconductor chip package.

19. A printed circuit board comprising a layer obtained by curing the adhesive film according to claim 15 or 16.

20. A semiconductor chip package comprising a layer obtained by curing the adhesive film according to claim 15 or 16.

21. A semiconductor device provided with the printed circuit board of claim 19 and/or the semiconductor chip package of claim 20.

22. A method for using the adhesive film according to claim 15 or 16, wherein the adhesive film is laminated under a pressure of 40MPa or less, and thereafter, a laminate or a semiconductor chip package is produced under a heating condition at a temperature of 220 ℃ or less.