WO2018003590A1

WO2018003590A1 - Heat-curable resin composition, resin film with carrier, printed wiring board, and semiconductor device

Info

Publication number: WO2018003590A1
Application number: PCT/JP2017/022627
Authority: WO
Inventors: 康二佐藤
Original assignee: 住友ベークライト株式会社
Priority date: 2016-06-28
Filing date: 2017-06-20
Publication date: 2018-01-04
Also published as: JP7028165B2; TW201821547A; JPWO2018003590A1

Abstract

The heat-curable resin composition according to the present invention is for use in forming an insulating layer of a printed wiring board, and comprises a heat-curable resin, a hardener, and an inorganic filler. The heat-curable resin composition gives a cured object which, in a dynamic viscoelasticity examination, has a 30ºC storage modulus E'₃₀ of 1-10 GPa and which, in a tensile test, has a tensile elongation of 2% or greater. It is preferable that the content of the inorganic filler in the heat-curable resin composition be 65-90 wt% with respect to the whole heat-curable resin composition.

Description

Thermosetting resin composition, resin film with carrier, printed wiring board, and semiconductor device

The present invention relates to a thermosetting resin composition, a resin film with a carrier, a printed wiring board, and a semiconductor device.

In the past, epoxy resin compositions have been developed in various ways from the viewpoint of reducing dimensional changes. As this type of technology, for example, an epoxy resin composition described in Patent Document 1 can be cited. As the epoxy resin of this epoxy resin composition, a bisphenol F type epoxy resin is used (paragraph 0124 of Patent Document 1, Example 2).

JP 2013-23667 A

However, the thinning of semiconductor packages in recent years is becoming more and more advanced. In light of such a development environment, the present inventors have examined and found that the cured product of the epoxy resin composition described in the above literature has room for improvement in terms of toughness.

The present inventor further examined the thermosetting resin composition used for forming the insulating layer in the printed wiring board, and focused on the elastic modulus and the elongation as characteristics related to toughness. As a result of further investigation, it has been found that excellent toughness can be realized by achieving both low elasticity and high elongation. And, by adopting the storage elastic modulus E ′ ₃₀ at 30 ° C. as the elastic modulus index, and adopting the tensile elongation measured by the tensile test as the elongation index, low elasticity and high elongation are obtained. It has been found that it can be evaluated optimally.

Based on these findings, a result of intensive studies, the storage modulus E _'30 of the cured product of the thermosetting resin composition is less than a predetermined value, and, by a tensile elongation greater than or equal to a predetermined value, heat It has been found that the toughness of the cured product of the curable resin composition can be improved, and the present invention has been completed.

According to the present invention,
A thermosetting resin composition used for forming an insulating layer in a printed wiring board,
A thermosetting resin;
A curing agent;
An inorganic filler,
When dynamic viscoelasticity measurement is performed on the cured product of the thermosetting resin composition, the storage elastic modulus E ′ ₃₀ at 30 ° C. of the cured product is 1 GPa or more and 10 GPa or less,
When a tensile test is performed on the cured product, a thermosetting resin composition having a tensile elongation of 2% or more is provided.

Also according to the invention,
A carrier substrate;
There is provided a resin film with a carrier comprising: a resin film formed of the thermosetting resin composition provided on the carrier substrate.

Also according to the invention,
A printed wiring board provided with an insulating layer composed of a cured product of a resin film of the thermosetting resin composition is provided.

Also according to the invention,
The printed wiring board;
There is provided a semiconductor device comprising a semiconductor element mounted on a circuit layer of the printed wiring board or built in the printed wiring board.

According to the present invention, a thermosetting resin from which an insulating layer having excellent toughness can be obtained, a resin film with a carrier using the same, a printed wiring board, and a semiconductor device are provided.

FIG. 1 is a cross-sectional view showing an example of the configuration of the resin film with a carrier in the present embodiment. 2A and 2B are cross-sectional views showing an example of the configuration of the printed wiring board in the present embodiment. 3A and 3B are cross-sectional views showing an example of the configuration of the semiconductor device in the present embodiment. 4A to 4C are process cross-sectional views illustrating an example of the manufacturing process of the printed wiring board in the present embodiment. FIG. 5 is a cross-sectional view showing an example of the configuration of the printed wiring board in the present embodiment. FIG. 6 is a cross-sectional view showing an example of the configuration of the printed wiring board in the present embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

The thermosetting resin composition of the present embodiment includes a thermosetting resin, a curing agent, and an inorganic filler. Moreover, when the thermosetting resin composition of this embodiment performs dynamic viscoelasticity measurement with respect to the hardened | cured material of the said thermosetting resin composition, the storage elastic modulus E 'of the said hardened | cured material in 30 degreeC. ₃₀ is less than 10GPa least 1 GPa, and, when subjected to tensile test with respect to the cured product, the tensile elongation of the cured product is at least 2%. Such a thermosetting resin composition is used for forming an insulating layer in a printed wiring board.

The present inventor has further studied a thermosetting resin composition used for forming an insulating layer in a printed wiring board, and has come to focus on storage elastic modulus and tensile elongation as characteristics relating to toughness. As a result of further investigation, in a cured product of a thermosetting resin composition containing a thermosetting resin, a curing agent, and an inorganic filler, it is excellent in achieving both low elasticity and high elongation. It has been found that toughness can be exhibited.

Result of studying in detail a method of evaluating the physical properties of the cured product of such a thermosetting resin composition, as an indicator of the elastic modulus, adopted storage modulus E _'30 at 30 ° C., as an index of elongation, tensile test It was found that low elasticity and high elongation can be optimally evaluated by adopting the tensile elongation measured by the above.

Although the detailed mechanism is not clear, in a three-dimensional network structure with a thermosetting resin, the crosslink point distance and the number of crosslink points are highly controlled, so that the crosslink density can be optimized, and low elasticity and high elongation can be achieved. It is thought that both can be achieved. For example, the use of a thermosetting resin having a large molecular weight per number of functional groups and a flexible skeleton, etc., controls the crosslink density and makes the storage elastic modulus and the tensile elongation rate within a desired numerical range. As mentioned.

As a result of intensive studies based on such knowledge, by setting the storage elastic modulus E ′ ₃₀ of the cured product of the thermosetting resin composition to 1 GPa or more and 10 GPa or less and the tensile elongation rate to 2% or more, The present inventors have found that the low elasticity and high elongation of the cured product of the thermosetting resin composition can be compatible and can exhibit excellent toughness, and the present invention has been completed.

In this embodiment, the insulating layer in the printed wiring board can be used as an insulating member constituting the printed wiring board such as a core layer, a build-up layer (interlayer insulating layer), a solder resist layer, and the like. The printed wiring board includes a core layer, a build-up layer (interlayer insulating layer), a printed wiring board having a solder resist layer, a printed wiring board having no core layer, a coreless board used for a panel package process (PLP), MIS (Molded Interconnect Substrate) substrate and the like.

The cured product of the resin film formed with the thermosetting resin composition of this embodiment is used for the insulating layer, for example, a build-up layer, a solder resist layer, or a PLP in a printed wiring board that does not have a core layer. It can also be used for an interlayer insulating layer and a solder resist layer of a coreless substrate, an interlayer insulating layer and a solder resist layer of a MIS substrate, and the like. As described above, the cured product of the resin film according to the present embodiment is a large-area printed wiring board used to collectively create a plurality of semiconductor packages. It can also be suitably used for the resist layer.

By using the cured resin film of this embodiment as an insulating layer, it has excellent toughness. Therefore, during panel level processes for manufacturing large panel size packages, panel (coreless substrate) warpage and during transport And substrate cracks during mounting can be suppressed.

Moreover, in the cured product of the resin film of the present embodiment, it becomes possible to highly fill the inorganic filler in the matrix resin having a flexible skeleton. Thereby, since the linear expansion coefficient of the hardened | cured material of the said resin film can be made low, the curvature of the semiconductor package obtained can fully be suppressed.

Each component of the thermosetting resin composition of the present embodiment will be described.

As described above, the thermosetting resin composition of the present embodiment includes, for example, a thermosetting resin, a curing agent, and an inorganic filler.

(Thermosetting resin)
As a thermosetting resin, an epoxy resin, a maleimide compound, etc. are mentioned, for example. These may be used alone or in combination of two or more. In the present embodiment, the thermosetting resin preferably contains at least an epoxy resin or a maleimide compound, and particularly preferably contains an epoxy resin.

Further, the thermosetting resin of the present embodiment is preferably liquid at 25 ° C. room temperature. Thereby, the dispersibility of each component in a thermosetting resin composition can be improved. Moreover, it becomes possible to raise the filling amount of an inorganic filler.

The lower limit of the viscosity at 25 ° C. of the thermosetting resin of this embodiment is, for example, 0.1 Pa · s or more, preferably 0.5 Pa · s or more, and preferably 1 Pa · s or more. More preferred. Thereby, the film-forming property of a thermosetting resin composition can be improved. On the other hand, the upper limit of the viscosity at 25 ° C. is, for example, 200 Pa · s or less, preferably 100 Pa · s or less, and more preferably 50 Pa · s or less. Thereby, the dispersibility of a thermosetting resin composition can be improved.

The lower limit of the epoxy equivalent of the epoxy resin of the present embodiment is, for example, 300 g / eq or more, preferably 330 g / eq or more, and more preferably 350 g / eq or more. Thereby, since a crosslinking point molecular weight can be controlled appropriately, the hardened | cured material of the thermosetting resin composition of the optimal crosslinking density is realizable. Moreover, the breaking elongation rate of the hardened | cured material of a thermosetting resin composition can be improved. On the other hand, the upper limit value of the epoxy equivalent is not particularly limited, but is, for example, 700 g / eq or less, preferably 600 g / eq or less, and more preferably 500 g / eq or less. Thereby, the intensity | strength of the hardened | cured material of a thermosetting resin composition can be improved.

The lower limit of the weight average molecular weight (Mw) of the epoxy resin of the present embodiment is not particularly limited, but is preferably Mw 300 or more, and more preferably Mw 800 or more. It can suppress that a tack | tuck arises in the hardened | cured material of a resin film as Mw is more than the said lower limit. The upper limit of Mw is not particularly limited, but is preferably Mw 20,000 or less, and more preferably Mw 15,000 or less. When Mw is not more than the above upper limit value, the handling property is improved and it becomes easy to form a resin film. The Mw of the epoxy resin can be measured by GPC, for example.

The epoxy resin of this embodiment is preferably liquid at 25 ° C. room temperature, and preferably contains at least one first epoxy resin having an epoxy equivalent in the above range.

The type of the first epoxy resin is not particularly limited, but for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy Resin, bisphenol type epoxy resin such as bisphenol Z type epoxy resin; phenol novolak type epoxy resin, cresol novolak type epoxy resin, tetraphenol group ethane type novolak type epoxy resin, novolak type epoxy resin having condensed ring aromatic hydrocarbon structure, etc. Novolac-type epoxy resins; biphenyl-type epoxy resins; aralkyl-type epoxy resins such as xylylene-type epoxy resins and biphenyl-aralkyl-type epoxy resins; naphthylene ether-type resins Naphthalene-type epoxy resins such as xylene resin, naphthol-type epoxy resin, naphthalenediol-type epoxy resin, bifunctional to tetrafunctional naphthalene-type epoxy resin, binaphthyl-type epoxy resin, naphthalene-aralkyl-type epoxy resin; anthracene-type epoxy resin; phenoxy-type epoxy resin Dicyclopentadiene type epoxy resin; norbornene type epoxy resin; adamantane type epoxy resin; fluorene type epoxy resin; polyether type epoxy resin. As a 1st epoxy resin, you may use these individually or in combination of 2 or more types. Among the first epoxy resins, from the viewpoint of viscosity, at least one selected from bisphenol A type epoxy resins, fluorene type epoxy resins, bifunctional naphthalene type epoxy resins, and polyether type epoxy resins can be used.

Further, as the epoxy resin of the present embodiment, in addition to the first epoxy resin, another second epoxy resin may be used in combination. The second epoxy resin can be selected from the types of epoxy resins mentioned as the first epoxy resin.

Among epoxy resins, bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthalene type from the viewpoint of further improving the heat resistance and insulation reliability of the obtained printed wiring board It is preferable to use one or more selected from an epoxy resin, an anthracene type epoxy resin, and a dicyclopentadiene type epoxy resin. It is more preferable to use one or more selected from aralkyl type epoxy resins, novolak type epoxy resins having a condensed ring aromatic hydrocarbon structure, and naphthalene type epoxy resins.

The lower limit of the content of the epoxy resin is preferably 3% by weight or more, more preferably 4% by weight or more, more preferably 5% by weight with respect to 100% by weight of the entire thermosetting resin composition (total solid content excluding the solvent). The above is more preferable. When the content of the epoxy resin is not less than the above lower limit value, handling properties are improved, and it becomes easy to form a resin film. On the other hand, the upper limit of the content of the epoxy resin is not particularly limited with respect to the entire thermosetting resin composition, but is preferably 60% by weight or less, more preferably 45% by weight or less, and more preferably 30% by weight or less. Further preferred. When the content of the epoxy resin is not more than the above upper limit, the strength and flame retardancy of the obtained printed wiring board are improved, the linear expansion coefficient of the printed wiring board is lowered, and the warp reduction effect is improved. There is a case.
In addition, the total solid content of a thermosetting resin composition refers to the whole component except the solvent contained in a thermosetting resin composition. The same applies hereinafter.

(Maleimide compound)
The thermosetting resin composition of this embodiment can contain a maleimide compound.
In this embodiment, the maleimide group of the maleimide compound has a five-membered planar structure. Moreover, the double bond of the maleimide group is easy to interact between molecules and has high polarity. Therefore, a strong intermolecular interaction is exhibited with a maleimide group, a benzene ring, other compounds having a planar structure, and the like, and molecular motion can be suppressed. Therefore, when the thermosetting resin composition contains a maleimide compound, the linear expansion coefficient of the obtained insulating layer can be lowered, the glass transition temperature can be improved, and the heat resistance can be further improved.

The maleimide compound is preferably a maleimide compound having at least two maleimide groups in the molecule.
Examples of the imide-expanded bismaleimide include a maleimide compound represented by the following formula (a1), a maleimide compound represented by the following formula (a2), a maleimide compound represented by the following formula (a3), and the like. Specific examples of the maleimide compound represented by the formula (a1) include BMI-1500 (manufactured by Designa Molecules Co., Ltd., molecular weight 1500). Specific examples of the maleimide compound represented by the formula (a2) include BMI-1700 (manufactured by Designer Molecules, molecular weight 1700), BMI-1400 (manufactured by Diginer Molecules, molecular weight 1400), and the like. . Specific examples of the maleimide compound represented by the formula (a3) include BMI-3000 (manufactured by Designa Molecules Co., Ltd., molecular weight 3000).

In the above formula (a1), n represents an integer of 1 or more and 10 or less.

In the above formula (a2), n represents an integer of 1 or more and 10 or less.

In the above formula (a3), n represents an integer of 1 or more and 10 or less.

The lower limit of the weight average molecular weight (Mw) of the maleimide compound is not particularly limited, but is preferably Mw 400 or more, and particularly preferably Mw 800 or more. When Mw is equal to or greater than the lower limit, it is possible to suppress the occurrence of tack in the insulating layer. Although the upper limit of Mw is not specifically limited, Mw4000 or less is preferable and Mw2500 or less is more preferable. When Mw is not more than the above upper limit value, handling properties are improved during the production of the insulating layer, and it becomes easy to form the insulating layer. The Mw of the maleimide compound can be measured, for example, by GPC (gel permeation chromatography, standard substance: converted to polystyrene).
The Mw of the imide-extended bismaleimide having maleimide at both ends can be regarded as the molecular weight between crosslinking points.

In the present embodiment, the content of the maleimide compound contained in the thermosetting resin composition is not particularly limited, but the total solid content of the thermosetting resin composition (that is, the component excluding the solvent) is 100% by weight. 1.0 wt% or more and 25.0 wt% or less is preferable, and 3.0 wt% or more and 20.0 wt% or less is more preferable. When the content of the maleimide compound is within the above range, the balance of low heat shrinkage and chemical resistance of the obtained insulating layer can be further improved.

(Benzoxazine compound)
The thermosetting resin composition of this embodiment may contain a benzoxazine compound.
A benzoxazine compound is a compound having a benzoxazine ring. As the benzoxazine compound, for example, one or more selected from a compound represented by the following formula (2) and a compound represented by the following formula (3) can be used.

(In the above formula (2), each X ₂ independently represents an alkylene group having 1 to 10 carbon atoms, a group represented by the following formula (1a), a group represented by “—SO ₂ —”, “—CO A group represented by “—”, an oxygen atom or a single bond, R ₂ is each independently a hydrocarbon group having 1 to 6 carbon atoms, and c is each independently an integer of 0 to 4).

(In the above formula (3), X ₃ each independently represents an alkylene group having 1 to 10 carbon atoms, a group represented by the following formula (1a), a group represented by “—SO ₂ —”, “—CO A group represented by “—”, an oxygen atom or a single bond, R ₃ is each independently a hydrocarbon group having 1 to 6 carbon atoms, and d is each independently an integer of 0 to 4).

(In the above formula (1a), Y is a hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring, and n ₂ is an integer of 0 or more.)

In the above formula (1a), the hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring may be composed only of an aromatic ring, or may have a hydrocarbon group other than the aromatic ring. Good. Y may have one aromatic ring or two or more aromatic rings. When Y has two or more aromatic rings, these aromatic rings may be the same or different. The aromatic ring may be a monocyclic structure or a polycyclic structure.
Examples of the hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring include aromatic compounds such as benzene, biphenyl, naphthalene, anthracene, fluorene, phenanthrene, indacene, terphenyl, acenaphthylene, and phenalene. And a divalent group obtained by removing two hydrogen atoms from the nucleus.
Moreover, these aromatic hydrocarbon groups may have a substituent. Here, that the aromatic hydrocarbon group has a substituent means that part or all of the hydrogen atoms constituting the aromatic hydrocarbon group are substituted by the substituent. Examples of the substituent include an alkyl group.
The alkyl group as the substituent is preferably a chain alkyl group. The number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, and a sec-butyl group.

Such a group Y preferably has a group obtained by removing two hydrogen atoms from benzene or naphthalene. Examples of the group represented by the above formula (1a) include the following formulas (1a-1), (1a-2) ) Is more preferable. Thereby, the insulating layer obtained from a thermosetting resin composition exhibits excellent heat resistance.

In the above formulas (1a-1) and (1a-2), R ₄ is each independently a hydrocarbon group having 1 to 6 carbon atoms. Each e is independently an integer of 0 or more and 4 or less, more preferably 0.

Further, in the group represented by the above formula (1a), n ₂ may be an integer of 0 or more, preferably an integer of 0 or more and 5 or less, and preferably an integer of 1 or more and 3 or less. More preferably, 1 or 2 is particularly preferable.

X ₂ and X ₃ in the above formula (2) and the above formula (3) are, for example, preferably independently a linear or branched alkylene group having 1 to 10 carbon atoms. Specific examples of the linear alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decanylene group, trimethylene group, tetramethylene group. Group, pentamethylene group, hexamethylene group and the like. Specific examples of the branched alkylene group include —C (CH ₃ ) ₂ — (isopropylene group), —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C Alkylmethylene groups such as (CH ₃ ) (CH ₂ CH ₃ ) —, —C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) —, —C (CH ₂ CH ₃ ) ₂ —; —CH (CH ₃ ) CH ₂ —, —CH (CH ₃ ) CH (CH ₃ ) —, —C (CH ₃ ) ₂ CH ₂ —, —CH (CH ₂ CH ₃ ) CH ₂ —, —C (CH ₂ CH ₃ ) ₂ Examples thereof include an alkylethylene group such as —CH ₂ —.
Further, the number of carbon atoms of the alkylene group in X ₂ and X ₃ may be 1 or more and 10 or less, more preferably 1 or more and 7 or less, and further preferably 1 or more and 3 or less. Specifically, examples of the alkylene group having such a carbon number include a methylene group, an ethylene group, a propylene group, and an isopropylene group.

In addition, R ₂ and R ₃ in the above formula (2) and the above formula (3) are, for example, each independently a hydrocarbon group having 1 to 6 carbon atoms, but a hydrocarbon having 1 or 2 carbon atoms. It is preferably a group, specifically a methyl group or an ethyl group.

Moreover, c and d in the above formula (2) and the above formula (3) are each independently an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 2 or less, and preferably 0. More preferred.

Such a benzoxazine compound is preferably a compound represented by the above formula (2) among the compound represented by the above formula (2) and the compound represented by the above formula (3). Thereby, the insulating layer obtained from a thermosetting resin composition can exhibit more excellent low heat shrinkability and chemical resistance.

In the compound represented by the formula (2), X ₂ is a linear or branched alkylene group having 1 to 3 carbon atoms, and R ₂ is a hydrocarbon group having 1 or 2 carbon atoms. And c is preferably an integer of 0 or more and 2 or less. Alternatively, X ₂ is a group represented by any one of formulas (1a-1) and (1a-2), and c is preferably 0. Thereby, the insulating layer obtained from a thermosetting resin composition can exhibit more excellent low heat shrinkability and chemical resistance.

Preferred specific examples of the benzoxazine compound include, for example, a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), a compound represented by the following formula (2-3), Examples thereof include one or more selected from a compound represented by (3-1), a compound represented by the following formula (3-2), and a compound represented by the following formula (3-3).

(In the above formula (2-3), each R is independently a hydrocarbon group having 1 to 4 carbon atoms.)

The content of the benzoxazine compound contained in the thermosetting resin composition is not particularly limited, but is 1 when the total solid content of the thermosetting resin composition (that is, the component excluding the solvent) is 100% by weight. 0.0 wt% or more and 25.0 wt% or less is preferable, and 3.0 wt% or more and 20.0 wt% or less is more preferable. When the content of the benzoxazine compound is within the above range, the low heat shrinkage and chemical resistance of the resulting insulating layer can be further improved.

(Inorganic filler)
The thermosetting resin composition of this embodiment can contain an inorganic filler.
Examples of inorganic fillers include silicates such as talc, calcined clay, unfired clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, silica, and fused silica; calcium carbonate, magnesium carbonate, and hydrotal Carbonates such as sites; hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite; zinc borate, barium metaborate, aluminum borate And borate salts such as calcium borate and sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride and carbon nitride; titanates such as strontium titanate and barium titanate.
Among these, talc, alumina, glass, silica, mica, aluminum hydroxide, and magnesium hydroxide are preferable, and silica is particularly preferable. As the inorganic filler, one of these may be used alone, or two or more may be used in combination.

Although the lower limit of the average particle diameter of the inorganic filler is not particularly limited, for example, 0.01 μm or more is preferable, 0.05 μm or more is more preferable, and 0.5 μm or more is more preferable. Thereby, it can suppress that the viscosity of the varnish of the said thermosetting resin becomes high, and can improve the workability | operativity at the time of insulation layer preparation. Moreover, the upper limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 5.0 μm or less, more preferably 2.0 μm or less, and further preferably 1.0 μm or less. Thereby, phenomena, such as sedimentation of the inorganic filler in the varnish of the said thermosetting resin, can be suppressed, and a more uniform resin film can be obtained. Moreover, when the circuit dimension L / S of the printed wiring board is less than 20 μm / 20 μm, it is possible to suppress the influence on the insulation between the wirings.
In the present embodiment, the average particle size of the inorganic filler is determined by measuring the particle size distribution of the particles on a volume basis using, for example, a laser diffraction particle size distribution measuring apparatus (LA-500, manufactured by HORIBA), and the median diameter (D50 ) May be the average particle size.

In the present embodiment, when the content of the inorganic filler is 65% by weight or more, the lower limit value of the average particle diameter of the inorganic filler is, for example, preferably 0.5 μm or more, and 0.6 μm or more. Is more preferable, and 0.8 μm or more is more preferable. On the other hand, the lower limit of the average particle diameter of the inorganic filler is, for example, preferably 2 μm or less, more preferably 1.9 μm or less, and even more preferably 1.8 μm or less. By setting the content of the inorganic filler within the above range, the strength can be further increased while reducing the warpage of the cured product of the resin film.

Further, the inorganic filler is not particularly limited, but an inorganic filler having a monodispersed average particle diameter may be used, or an inorganic filler having a polydispersed average particle diameter may be used. Furthermore, one type or two or more types of inorganic fillers having an average particle size of monodispersed and / or polydispersed may be used in combination.

The inorganic filler preferably contains silica particles. The average particle diameter of the silica particles is not particularly limited, but is preferably 5.0 μm or less, more preferably 0.1 μm or more and 4.0 μm or less, and further preferably 0.2 μm or more and 2.0 μm or less. When the average particle diameter of the silica particles used is within the above range, the filling property of the inorganic filler into the resin film can be further improved.

The lower limit of the content of the inorganic filler is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, for example, preferably 65% by weight or more, more preferably 70% by weight or more, More preferably 75% by weight or more. Thereby, while being able to make especially low the thermal expansion coefficient of the hardened | cured material of a resin film, the water absorption rate can be made especially low. Thereby, the curvature of a semiconductor package can be suppressed. Moreover, since the cured product of the resin film of the present embodiment can increase the content of the inorganic filler while maintaining a high elongation rate, the stress relaxation property can be improved. On the other hand, the upper limit of the content of the inorganic filler is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, but is preferably 98% by weight or less, for example, 95% by weight. % Or less, more preferably 90% by weight or less. When the content of the inorganic filler is within the above range, the workability of the cured product of the resin film can be improved.

(Curing agent)
The thermosetting resin composition of the present embodiment can contain a curing agent.
The curing agent is not particularly limited. For example, tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2- Ethyl-4-methylimidazole (EMI24), 2-phenyl-4-methylimidazole (2P4MZ), 2-phenylimidazole (2PZ), 2-phenyl-4-methyl-5-hydroxyimidazole (2P4MHZ), 1-benzyl- imidazole compounds such as 2-phenylimidazole (1B2PZ); catalyst type curing agents include Lewis acids such as BF ₃ complex.
Also, for example, aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), m-phenylenediamine, p-phenylenediamine, o-xylenediamine, 4,4′- Diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 4,4'- (P-phenylenediisopropylidene) dianiline, 2,2- [4- (4-aminophenoxy) phenyl] propane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-diamino-3 , 3'-diethyl-5,5'-dimethyldiphenylmethane, 3 In addition to aromatic polyamines such as 3'-diethyl-4,4'-diaminodiphenylmethane, polyamine compounds including dicyandiamide (DICY), organic acid dihydrazide, etc .; hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA) Acid anhydrides including aromatic acid anhydrides such as alicyclic acid anhydrides such as, trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); polysulfide, thioester, Polymercaptan compounds such as thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; polyaddition type curing agents such as organic acids such as carboxylic acid-containing polyester resins; 2,2′-methylenebis (4-ethyl-6- t ert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3- Methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butylhydroquinone, 1,3,5-tris (3,5-di-tert) Phenolic compounds such as -butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) trione can also be used.
Furthermore, as the second curing agent, for example, a phenol resin-based curing agent such as a novolak type phenol resin or a resol type phenol resin; a urea resin such as a methylol group-containing urea resin; a melamine resin such as a methylol group-containing melamine resin; A condensation type curing agent may also be used. These may be used alone or in combination of two or more.

The phenol resin-based curing agent is a monomer, oligomer, or polymer in general having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol novolak resin, Novolak type phenolic resin such as naphthol novolak resin; polyfunctional phenolic resin such as triphenolmethane type phenolic resin; modified phenolic resin such as terpene modified phenolic resin and dicyclopentadiene modified phenolic resin; phenylene skeleton and / or biphenylene skeleton Aralkyl resins such as phenol aralkyl resins, naphthol aralkyl resins having a phenylene and / or biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F Etc. The. These may be used alone or in combination of two or more. Among these, from the viewpoint of curability, a phenol resin-based curing agent having a hydroxyl group equivalent of 90 g / eq or more and 250 g / eq or less may be used.
The weight average molecular weight of the phenol resin is not particularly limited, but the weight average molecular weight is preferably 4 × 10 ² or more and 1.8 × 10 ³ or less, more preferably 5 × 10 ² or more and 1.5 × 10 ³ or less. By making the weight average molecular weight equal to or higher than the above lower limit value, problems such as tackiness occur in the prepreg, and by making the above upper limit value or less, the impregnation property to the fiber base material is improved at the time of prepreg production, A more uniform product can be obtained.

The lower limit of the content of the curing agent is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, but is preferably 0.01% by weight or more, for example, 0.05% by weight or more. More preferred is 0.2% by weight or more. By setting the content of the curing agent to the above lower limit value or more, the effect of promoting curing can be sufficiently exhibited. On the other hand, the upper limit of the content of the curing agent is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, but is preferably 15% by weight or less, and more preferably 10% by weight or less. 8% by weight or less is more preferable. The preservability of a prepreg can be improved more as content of a hardening | curing agent is below the said upper limit.

(Cyanate resin)
The thermosetting resin composition of the present embodiment can further contain a cyanate resin.
The cyanate resin is a resin having a cyanate group (—O—CN) in the molecule, and a resin having two or more cyanate groups in the molecule can be used. Such a cyanate resin is not particularly limited. For example, it can be obtained by reacting a halogenated cyanide compound with phenols or naphthols, and prepolymerizing by a method such as heating as necessary. Moreover, the commercial item prepared in this way can also be used.
By using cyanate resin, the linear expansion coefficient of the cured resin film can be reduced. Furthermore, the electrical properties (low dielectric constant, low dielectric loss tangent), mechanical strength, etc. of the cured resin film can be enhanced.

Examples of the cyanate resin include novolak type cyanate resin; bisphenol type cyanate resin, bisphenol E type cyanate resin, bisphenol type cyanate resin such as tetramethylbisphenol F type cyanate resin; reaction of naphthol aralkyl type phenol resin and cyanogen halide. Naphthol aralkyl type cyanate resin obtained by the following: dicyclopentadiene type cyanate resin; biphenylalkyl type cyanate resin. Among these, novolak type cyanate resins and naphthol aralkyl type cyanate resins are preferable, and novolak type cyanate resins are more preferable. By using the novolac-type cyanate resin, the crosslink density of the cured product of the resin film is increased, and the heat resistance is improved.

The reason for this is that the novolac-type cyanate resin forms a triazine ring after the curing reaction. Furthermore, it is considered that novolak-type cyanate resin has a high benzene ring ratio due to its structure and is easily carbonized. Moreover, the cured product of the resin film containing the novolak type cyanate resin has excellent rigidity. Therefore, the heat resistance of the cured resin film can be further improved.

As the novolac-type cyanate resin, for example, a resin represented by the following general formula (I) can be used.

The average repeating unit n of the novolak cyanate resin represented by the general formula (I) is an arbitrary integer. The average repeating unit n is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. When the average repeating unit n is not less than the above lower limit, the heat resistance of the novolak cyanate resin is improved, and it is possible to suppress the demerization and volatilization of the low mer during heating. The average repeating unit n is not particularly limited, but is preferably 10 or less, more preferably 7 or less. It can suppress that melt viscosity becomes it high that n is below the said upper limit, and can improve the moldability of a resin film.

As the cyanate resin, a naphthol aralkyl type cyanate resin represented by the following general formula (II) is also preferably used. The naphthol aralkyl type cyanate resin represented by the following general formula (II) includes, for example, naphthols such as α-naphthol or β-naphthol, p-xylylene glycol, α, α'-dimethoxy-p-xylene, 1,4 A resin obtained by condensing a naphthol aralkyl type phenol resin obtained by reaction with di (2-hydroxy-2-propyl) benzene or the like and cyanogen halide. The repeating unit n in the general formula (II) is preferably an integer of 10 or less. When the repeating unit n is 10 or less, a more uniform resin film can be obtained. In addition, intramolecular polymerization hardly occurs at the time of synthesis, the liquid separation property at the time of washing with water tends to be improved, and the decrease in yield tends to be prevented.

(In the formula, each R independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more and 10 or less.)

In addition, one kind of cyanate resin may be used alone, two or more kinds may be used in combination, and one kind or two or more kinds and a prepolymer thereof may be used in combination.

The lower limit of the content of the cyanate resin is, for example, preferably 1% by weight or more, more preferably 2% by weight or more, and further more preferably 3% by weight or more with respect to 100% by weight of the total solid content of the thermosetting resin composition. preferable. It is possible to achieve low linear expansion and high elastic modulus of the cured resin film. On the other hand, the upper limit of the content of the cyanate resin is not particularly limited with respect to 100% by weight of the total solid content of the thermosetting resin composition, but is preferably 30% by weight or less, and more preferably 25% by weight or less. 20% by weight or less is more preferable. Heat resistance and moisture resistance can be improved. Further, when the content of the cyanate resin is within the above range, the storage elastic modulus E ′ of the cured product of the resin film can be further improved.

(Phenoxy resin)
The thermosetting resin composition of this embodiment may contain a phenoxy resin, for example.

Examples of the phenoxy resin include a phenoxy resin having a bisphenol skeleton, a phenoxy resin having a naphthalene skeleton, a phenoxy resin having an anthracene skeleton, and a phenoxy resin having a biphenyl skeleton. A phenoxy resin having a structure having a plurality of these skeletons can also be used.

Among these, it is preferable to use a phenoxy resin having a biphenyl skeleton and a bisphenol S skeleton as the phenoxy resin. The rigidity of the biphenyl skeleton can increase the glass transition temperature of the phenoxy resin, and the presence of the bisphenol S skeleton can improve the adhesion between the phenoxy resin and the metal. As a result, the heat resistance of the insulating layer can be improved, and the adhesion of the wiring layer to the insulating layer can be improved. It is also preferable to use a phenoxy resin having a bisphenol A skeleton and a bisphenol F skeleton as the phenoxy resin. Thereby, the adhesiveness of a wiring layer and an insulating layer can further be improved.
It is also preferable to use a phenoxy resin having a bisphenolacetophenone structure represented by the following general formula (X).

(In the formula (X), R ₁ may be the being the same or different, a hydrogen atom, a group selected from a hydrocarbon group or a halogen element 1 to 10 carbon atoms, R ₂ is A group selected from a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, R ₃ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and m is 0 to 5 (It is an integer.)

Since the phenoxy resin containing a bisphenol acetophenone structure has a bulky structure, it has excellent solvent solubility and compatibility with the thermosetting resin component to be blended. In addition, since a uniform rough surface can be formed with low roughness, the SAP characteristics of the insulating layer can be improved.

The phenoxy resin having a bisphenolacetophenone structure can be synthesized by a known method such as a method of increasing the molecular weight of an epoxy resin and a phenol resin using a catalyst.

The phenoxy resin having a bisphenol acetophenone structure may contain a structure other than the bisphenol acetophenone structure of the general formula (X), and the structure is not particularly limited, but bisphenol A type, bisphenol F type, bisphenol S type, biphenyl Type, phenol novolac type, cresol novolac type structure and the like. Among them, a phenoxy resin containing a biphenyl type structure as a structure other than the bisphenol acetophenone structure is preferable because of its high glass transition temperature.

The content of the bisphenolacetophenone structure of the general formula (X) in the phenoxy resin containing a bisphenolacetophenone structure is not particularly limited, but is preferably 5 mol% or more and 95 mol% or less, and preferably 10 mol% or more and 85 mol% or less. More preferably, it is 15 mol% or more and 75 mol% or less. The effect which improves heat resistance and moisture-proof reliability can fully be exhibited as content is more than the said lower limit. Moreover, solvent solubility can be improved as content is below the said upper limit.

The lower limit of the weight average molecular weight (Mw) of the phenoxy resin is, for example, preferably 10,000 or more, more preferably 15,000 or more, and further preferably 20,000 or more. Thereby, the compatibility with other resin and the solubility to a solvent can be improved. On the other hand, the upper limit value of the weight average molecular weight (Mw) of the phenoxy resin is, for example, preferably 60,000 or less, more preferably 55,000 or less, and further preferably 50,000 or less. Thereby, the film formability of an insulating layer improves and it can suppress that a malfunction generate | occur | produces, when using it for manufacture of a printed wiring board.

The content of the phenoxy resin is not particularly limited, but is preferably 0.5% by weight or more and 40% by weight or less, and preferably 1% by weight or more and 20% by weight or less with respect to the entire thermosetting resin composition excluding the inorganic filler. % Or less is more preferable. When the content is equal to or higher than the lower limit, it is possible to suppress a decrease in mechanical strength of the insulating layer and a decrease in plating adhesion between the insulating layer and the conductor circuit. When it is not more than the above upper limit, an increase in the coefficient of thermal expansion of the insulating layer can be suppressed, and a decrease in heat resistance can be suppressed.

(Curing accelerator)
The thermosetting resin composition of this embodiment may contain a hardening accelerator, for example. Thereby, the sclerosis | hardenability of a thermosetting resin composition can be improved. As a hardening accelerator, the compound which accelerates | stimulates hardening reaction of a thermosetting resin can be used, The kind is not specifically limited. In this embodiment, as a hardening accelerator, for example, zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, zinc octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III) Organic metal salts such as triethylamine, tributylamine, tertiary amines such as diazabicyclo [2,2,2] octane, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, Imidazoles such as 2-phenyl-4-ethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxyimidazole , Phenol, bisphe Lumpur A, phenolic compounds nonylphenol, acetic, benzoic acid, salicylic, organic acids such as p-toluenesulfonic acid, and one or more selected from an onium salt compound. Among these, it is more preferable to include an onium salt compound from the viewpoint of more effectively improving curability.

Although the onium salt compound used as a curing accelerator is not particularly limited, for example, a compound represented by the following general formula (2) can be used.

(In formula (2), P is a phosphorus atom, R ³ , R ⁴ , R ⁵ and R ⁶ are each an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. represents a group, optionally being the same or different .A ^- is an anion of n (n ≧ 1) number of proton donor having a proton capable of releasing the extracellular molecules in at least one or more intramolecular or, Indicates the complex anion)

The lower limit of the content of the curing accelerator is, for example, preferably 0.01% by weight or more and more preferably 0.05% by weight or more with respect to 100% by weight of the total solid content of the thermosetting resin composition. . By making content of a hardening accelerator more than the said lower limit, sclerosis | hardenability of a thermosetting resin composition can be improved more effectively. On the other hand, the upper limit value of the content of the curing accelerator is, for example, preferably 2.5% by weight or less and more preferably 1% by weight or less with respect to 100% by weight of the total solid content of the thermosetting resin composition. By making content of a hardening accelerator into the said upper limit or less, the preservability of a thermosetting resin composition can be improved.

(Coupling agent)
The thermosetting resin composition of this embodiment may contain a coupling agent. The coupling agent may be added directly when preparing the thermosetting resin composition, or may be added in advance to the inorganic filler. Use of a coupling agent can improve the wettability of the interface between the inorganic filler and each resin. Therefore, it is preferable to use a coupling agent, and the heat resistance of the cured resin film can be improved. Moreover, adhesiveness with copper foil can be improved by using a coupling agent. Furthermore, since the moisture absorption resistance can be improved, the adhesion with the copper foil can be maintained even after the humidity environment.

Examples of the coupling agent include silane coupling agents such as epoxy silane coupling agents, cationic silane coupling agents, and amino silane coupling agents, titanate coupling agents, and silicone oil type coupling agents. A coupling agent may be used individually by 1 type, and may use 2 or more types together. In this embodiment, the coupling agent may contain a silane coupling agent.
Thereby, the wettability of the interface of an inorganic filler and each resin can be made high, and the heat resistance of the hardened | cured material of a resin film can be improved more.

The silane coupling agent is not particularly limited, and examples thereof include epoxy silane, amino silane, alkyl silane, ureido silane, mercapto silane, and vinyl silane.

Specific examples of the compound include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-amino. Propylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (aminohexyl) 3-aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldimethoxysilane, β- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, γ-ureidopropyltriethoxysilane, vinyltriethoxysilane, etc., one or a combination of two or more of these Of these, epoxy silane, mercapto silane, and amino silane are preferable, and the amino silane is more preferably primary amino silane or anilino silane.

The addition amount of the coupling agent can be appropriately adjusted with respect to the specific surface area of the inorganic filler. The lower limit of the amount of coupling agent added is, for example, preferably 0.01% by weight or more, more preferably 0.05% by weight or more with respect to 100% by weight of the total solid content of the thermosetting resin composition. preferable. When the content of the coupling agent is not less than the above lower limit, the inorganic filler can be sufficiently covered, and the heat resistance of the cured product of the resin film can be improved. On the other hand, the upper limit of the addition amount of the coupling agent is preferably, for example, 3% by weight or less, more preferably 1.5% by weight or less, with respect to 100% by weight of the total solid content of the thermosetting resin composition. When the content of the coupling agent is not more than the above upper limit value, it is possible to suppress the influence on the reaction, and it is possible to suppress a decrease in the bending strength or the like of the cured product of the resin film.

(Additive)
The thermosetting resin composition of the present embodiment is a dye such as green, red, blue, yellow, and black, a pigment such as a black pigment, and a dye within a range that does not impair the object of the present invention. One or more colorants, low-stress agents, antifoaming agents, leveling agents, UV absorbers, foaming agents, antioxidants, flame retardants, ion scavengers, and other components (thermosetting resins, curing agents, inorganic fillers) Additives other than materials, curing accelerators, and coupling agents) may be included. These may be used alone or in combination of two or more.

The thermosetting resin composition of the present embodiment may not contain a low stress agent or a rubber component. Even in this case, the cured product of the thermosetting resin composition of the present embodiment can be made to have a low elastic modulus while increasing the filling rate of the inorganic filler, so that it is caused by warpage during the substrate process or impact during transportation. Cracks can be suppressed.

Examples of pigments include kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, strontium yellow, hydrous chromium oxide, chromium oxide, cobalt aluminate, synthetic ultramarine blue, etc., polycyclic pigments such as phthalocyanine, azo pigments Etc.

Examples of the dye include isoindolinone, isoindoline, quinophthalone, xanthene, diketopyrrolopyrrole, perylene, perinone, anthraquinone, indigoid, oxazine, quinacridone, benzimidazolone, violanthrone, phthalocyanine, azomethine and the like.

In this embodiment, the varnish-like thermosetting resin composition can contain a solvent.
Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol, anisole, and N -Organic solvents such as methylpyrrolidone. These may be used alone or in combination of two or more.

When the thermosetting resin composition is varnished, the solid content of the thermosetting resin composition is preferably, for example, 30% by weight to 80% by weight, and more preferably 40% by weight to 70% by weight. . Thereby, the thermosetting resin composition excellent in workability | operativity and film formability is obtained.

The varnish-like thermosetting resin composition comprises the above-described components, for example, an ultrasonic dispersion method, a high-pressure collision dispersion method, a high-speed rotation dispersion method, a bead mill method, a high-speed shear dispersion method, and a rotation and revolution dispersion method. It can prepare by melt | dissolving in a solvent, mixing, and stirring using various mixers of these.

Next, the resin film of this embodiment will be described.

The resin film of the present embodiment can be obtained by forming a film of the thermosetting resin composition having a varnish shape. For example, the resin film of this embodiment can be obtained by removing the solvent from the coating film obtained by coating a varnish-like thermosetting resin composition. In such a resin film, the solvent content can be 5% by weight or less based on the entire resin film. In the present embodiment, for example, a step of removing the solvent may be performed under conditions of 100 ° C. to 150 ° C. and 1 minute to 5 minutes. Thereby, it is possible to sufficiently remove the solvent while suppressing the curing of the resin film containing the thermosetting resin.

(Resin film with carrier)
Next, the resin film with a carrier of this embodiment will be described.
FIG. 1 is a cross-sectional view showing an example of the configuration of the resin film with carrier 100 in the present embodiment.
As shown in FIG. 1, the resin film with a carrier 100 of the present embodiment includes a carrier base material 12 and a resin film 10 formed on the carrier base material 12 and formed from the thermosetting resin composition. Can be provided. Thereby, the handleability of the resin film 10 can be improved.

The resin film with carrier 100 may be a roll shape that can be wound or a single wafer shape such as a rectangular shape.

In the present embodiment, for example, a polymer film or a metal foil can be used as the carrier substrate 12. The polymer film is not particularly limited. For example, polyolefin such as polyethylene and polypropylene, polyester such as polyethylene terephthalate and polybutylene terephthalate, release paper such as polycarbonate and silicone sheet, heat resistance such as fluorine resin and polyimide resin. A thermoplastic resin sheet having The metal foil is not particularly limited. For example, copper or copper alloy, aluminum or aluminum alloy, iron or iron alloy, silver or silver alloy, gold or gold alloy, zinc or zinc alloy, nickel Alternatively, a nickel-based alloy, tin, a tin-based alloy, or the like can be given. Among these, a sheet made of polyethylene terephthalate is most preferable because it is inexpensive and easy to adjust the peel strength. By using a sheet made of such a material as the carrier substrate 12, it becomes easy to peel the resin film 10 from the carrier substrate 12 with an appropriate strength.

The lower limit of the thickness of the resin film 10 is not particularly limited, but is preferably 1 μm or more, more preferably 3 μm or more, and further preferably 5 μm or more. Thereby, the mechanical strength of the resin film 10 can be increased. On the other hand, the upper limit value of the thickness of the resin film 10 is not particularly limited, but is preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less. Thereby, the semiconductor device can be thinned.

The thickness of the carrier substrate is not particularly limited, but is preferably 10 to 100 μm, for example, and more preferably 10 to 70 μm. Thereby, the handleability at the time of manufacturing the resin film 100 with a carrier becomes more favorable.

The resin film with carrier 100 of the present embodiment may be a single layer or a multilayer, and may include one or more types of resin films 10. When the resin sheet is multi-layered, the resin sheets may be composed of the same kind or different kinds. The resin film with carrier 100 may have a protective film on the outermost layer side on the resin film 10.

In the present embodiment, the method for forming the resin film with carrier 100 is not particularly limited. As such a method, for example, a coating film is formed by applying a varnish-like thermosetting resin composition on the carrier substrate 12 using various coater apparatuses, and then the coating film is appropriately dried. Can be used to remove the solvent.

The characteristics of the resin film of this embodiment will be described.

As described above, the resin film of the present embodiment is a resin film formed from the thermosetting resin composition.
Since the cured product of the resin film of the present embodiment can achieve both low elastic properties and high elongation properties, excellent toughness can be realized.

When dynamic viscoelasticity measurement is performed on the cured product of the thermosetting resin composition in the present embodiment, the upper limit value of the storage elastic modulus E ′ ₃₀ at 30 ° C. of the cured product is 10 GPa or less. , 9 GPa or less is preferable, and 8 GPa or less is more preferable. Thereby, the hardened | cured material of the resin film excellent in low elasticity is realizable. On the other hand, the lower limit value of the storage elastic modulus E ′ ₃₀ at 30 ° C. is 1 GPa or more. Thereby, since a predetermined elastic modulus is obtained, a cured product of the resin film having excellent strength can be obtained.

When a tensile test is performed on the cured product of the thermosetting resin composition in the present embodiment, the lower limit value of the tensile elongation rate of the cured product is 2% or more, preferably 3% or more. More preferably, it is 4% or more. Thereby, the cured | curing material of the resin film excellent in the softness | flexibility and extensibility is obtained. In addition, a cured product of a resin film having high elongation while being highly filled with an inorganic filler can be obtained. On the other hand, the upper limit value of the tensile elongation is not particularly limited, but may be 40% or less, for example.
In the present embodiment, since the tensile elongation can be increased while reducing the storage elastic modulus, a cured resin film having excellent toughness can be obtained.

In this embodiment, the lower limit of the glass transition temperature of the cured product of the thermosetting resin composition is not particularly limited, but is preferably 10 ° C. or higher, more preferably 15 ° C. or higher, and further preferably 20 ° C. or higher. By setting the glass transition temperature of the cured product within the range of room temperature 25 ° C. ± about 10 ° C., the elastic properties and elongation properties of the cured product at the actual temperature are more excellent. Thereby, the curvature and crack of a board | substrate at the time of conveyance can fully be suppressed. Moreover, although the upper limit of the said glass transition temperature is not specifically limited, For example, it is good also as 220 degrees C or less, 110 degrees C or less is more preferable, 80 degrees C or less is more preferable, and 35 degrees C or less is further more preferable.

In the present embodiment, the lower limit of the peak value of the loss tangent tan δ of the cured product of the thermosetting resin composition is, for example, preferably 0.25 or more, more preferably 0.3 or more, and further preferably 0.45 or more. . Thereby, since the said hardened | cured material can absorb energy, the influence by the stress etc. resulting from the expansion coefficient difference between members can be made small, and a substrate crack can be suppressed. By setting the lower limit value of the peak value of the loss tangent tan δ to 0.5 or more, it is possible to realize very excellent elongation. On the other hand, the upper limit value of the peak value of the loss tangent tan δ is not particularly limited, but is preferably 1 or less, more preferably 0.95 or less, and still more preferably 0.9 or less.

Further, the lower limit of the half-value width of the peak value of the loss tangent tan δ of the cured product of the thermosetting resin composition is, for example, preferably 20 or more, more preferably 30 or more, and further preferably 35 or more. Thereby, the energy absorptivity of the said hardened | cured material with respect to a temperature change can be improved. On the other hand, the upper limit of the half width of the peak of the loss tangent tan δ is not particularly limited, but is preferably 100 or less, more preferably 90 or less, and still more preferably 80 or less. Thereby, since the change of the elasticity modulus of the said hardened | cured material with respect to a temperature change can be suppressed, connection reliability can be improved.

The glass transition temperature, loss tangent tan δ, and storage elastic modulus can be measured using a dynamic viscoelasticity analyzer (DMA). The glass transition temperature is a temperature at which the loss tangent tan δ has a maximum value in a curve obtained by dynamic viscoelasticity measurement under conditions of a temperature rising rate of 5 ° C./min and a frequency of 1 Hz. The loss tangent tan δ and the storage elastic modulus are calculated as a loss tangent tan δ and a storage elastic modulus E ′ ₃₀ at 30 ° C. by dynamic viscoelasticity measurement under conditions of a temperature rising rate of 5 ° C./min and a frequency of 1 Hz. it can.

In this embodiment, the glass transition temperature, the loss tangent tan δ, and the storage elastic modulus are set to a frequency using, for example, a dynamic viscoelasticity measuring device for a cured resin film obtained by heat treatment at 200 ° C. for 2 hours. It can be calculated from a measurement result obtained by performing a dynamic viscoelasticity test under the conditions of 1 Hz and a heating rate of 5 ° C./min. Although it does not specifically limit as a dynamic viscoelasticity measuring apparatus, For example, a DMA apparatus (TA instrument company make, Q800) can be used.

In this embodiment, the tensile elongation rate can be measured as follows. First, a cured product of a resin film obtained by heat treatment at 200 ° C. for 2 hours is cut into a test piece of length 100 mm × width 6 mm. In the tensile test, evaluation is performed by holding the test piece between chucks arranged at a constant distance and pulling the test piece at a constant speed until the test piece breaks. At this time, using a precision universal testing machine (manufactured by Shimadzu Corp., Autograph AG-IS), initial chuck distance L: 20 mm, test piece thickness: 0.1 mm, measurement temperature: 25 ° C., test speed: 1 mm Use the conditions per minute. In the tensile test, the tensile elongation percentage (%) is calculated from the amount of displacement when fractured under the above conditions and the initial inter-chuck distance.

In this embodiment, the upper limit value of the average linear expansion coefficient calculated in the range of 50 ° C. to 250 ° C. of the cured resin film is, for example, preferably 120 ppm / ° C. or less, more preferably 110 ppm / ° C. or less, and 90 ppm / More preferably, it is not higher than ° C. Thereby, the curvature of the printed wiring board during a manufacturing process can be reduced. Further, the warpage of the obtained semiconductor package can be reduced. On the other hand, the lower limit value of the average linear expansion coefficient is not particularly limited, but is preferably 1 ppm / ° C or more, and more preferably 10 ppm / ° C or more.

The linear expansion coefficient can be measured using, for example, a thermomechanical analyzer TMA. Specifically, the linear expansion coefficient is determined by using, for example, a thermomechanical analyzer TMA (TA Instruments, Q400), a temperature range of 50 to 250 ° C., a temperature rising rate of 10 ° C./min, a load of 10 g, Thermomechanical analysis (TMA) is measured for 2 cycles under the tension mode condition. The average value of the linear expansion coefficients in the plane direction (XY direction) in the range of 50 ° C. to 250 ° C. is calculated. In addition, the value of the 2nd cycle is employ | adopted for a linear expansion coefficient.

In the present embodiment, for example, by appropriately selecting the types and blending ratios of components constituting the thermosetting resin composition, the storage elastic modulus and the tensile elongation of the cured product of the thermosetting resin composition are each selected. The rate can be within a desired range. Among these, for example, by using a thermosetting resin having a large molecular weight per functional group and having a flexible skeleton, the cross-linking density of the cured product can be controlled by the storage elastic modulus and the tensile elongation rate. As an element to make the desired numerical range

(Printed circuit board)
The printed wiring board of this embodiment includes an insulating layer composed of a cured product of the above resin film (cured product of a thermosetting resin composition).
In the present embodiment, the cured product of the resin film is, for example, a core layer, a buildup layer, a solder resist layer of a normal printed wiring board, a buildup layer, a solder resist layer, or a PLP in a printed wiring board having no core layer. It can be used for an interlayer insulating layer and a solder resist layer of a coreless substrate used, an interlayer insulating layer and a solder resist layer of a MIS substrate, and the like. Such an insulating layer is preferably used for an interlayer insulating layer and a solder resist layer constituting the printed wiring board in a large-area printed wiring board used to collectively create a plurality of semiconductor packages. it can.

Next, an example of the printed wiring board 300 according to the present embodiment will be described with reference to FIGS.
The printed wiring board 300 of this embodiment includes an insulating layer made of a cured product of the resin film 10 described above. As shown in FIG. 2A, the printed wiring board 300 may have a structure including an insulating layer 301 (core layer) and an insulating layer 401 (solder resist layer). Further, as shown in FIG. 2B, the printed wiring board 300 has a structure including an insulating layer 301 (core layer), an insulating layer 305 (build-up layer), and an insulating layer 401 (solder resist layer). It may be. Each of these core layer, build-up layer, and solder resist layer can be composed of, for example, a cured product of the resin film of the present embodiment. This core layer may be composed of a cured body obtained by curing a prepreg formed by impregnating a fiber base material with the thermosetting resin composition of the present embodiment.

The cured product formed of the resin film of the present embodiment may not include a fiber substrate such as a glass cloth or a paper substrate. Thereby, it can be set as the structure especially suitable in order to form a buildup layer (interlayer insulation layer) and a soldering resist layer.

Also, the printed wiring board 300 according to the present embodiment may be a single-sided printed wiring board, a double-sided printed wiring board, or a multilayer printed wiring board. A double-sided printed wiring board is a printed wiring board in which a metal layer 303 is laminated on both sides of an insulating layer 301. The multilayer printed wiring board is a printed wiring board in which two or more build-up layers (for example, the insulating layer 305) are stacked on the insulating layer 301 as a core layer by a plated through hole method, a build-up method, or the like. .

In the present embodiment, the via hole 307 may be a hole for electrically connecting layers, and may be either a through hole or a non-through hole. The via hole 307 may be formed by embedding a metal. The buried metal may have a structure covered with an electroless metal plating film 308.

In the present embodiment, the metal layer 303 may be, for example, a circuit pattern or an electrode pad. The metal layer 303 may have, for example, a metal laminated structure of the metal foil 105 and the electrolytic metal plating layer 309.
The metal layer 303 is, for example, on the surface of an insulating layer (for example, the insulating layer 301 or the insulating layer 305) formed of the metal foil 105 that has been subjected to chemical treatment or plasma treatment or a cured product of the resin film of the present embodiment. It is formed by the SAP (semi-additive process) method. For example, after the electroless metal plating film 308 is applied on the metal foil 105 or the insulating

layers

301 and 305, the non-circuit forming portion is protected by a plating resist, and the electrolytic metal plating layer 309 is applied by electrolytic plating. The metal layer 303 is formed by patterning the electrolytic metal plating film 309 by removal and flash etching.

Further, the printed wiring board 300 of the present embodiment can be a resin board that does not contain glass fiber. For example, the insulating layer 301 that is the core layer may be configured not to contain glass fibers. Even in a semiconductor package using such a resin substrate, the linear expansion coefficient of the cured product of the resin film can be reduced, so that package warpage can be sufficiently suppressed.

(Semiconductor package)
Next, the semiconductor device 400 of this embodiment will be described. FIGS. 3A and 3B are cross-sectional views illustrating an example of the configuration of the semiconductor device 400.
The semiconductor device 400 of this embodiment can include a printed wiring board 300 and a semiconductor element mounted on the circuit layer of the printed wiring board 300 or built in the printed wiring board 300.

For example, the semiconductor device 400 shown in FIG. 3A has a structure in which the semiconductor element 407 is mounted on the circuit layer (metal layer 303) of the printed wiring board 300 shown in FIG. On the other hand, the semiconductor device 400 shown in FIG. 3B has a structure in which the semiconductor element 407 is mounted on the circuit layer (metal layer 303) of the printed wiring board 300 shown in FIG. The semiconductor element 407 is covered with a sealing material layer 413. Such a semiconductor package may have a flip chip structure in which the semiconductor element 407 is electrically connected to the printed wiring board 300 via the solder bump 410 and the metal layer 303.

In the present embodiment, the structure of the semiconductor package is not limited to the flip chip connection structure, and may have various structures. For example, a fan-out structure may be used. The insulating layer formed of the cured resin film of the present embodiment can suppress substrate warpage and substrate cracks in the manufacturing process of a semiconductor package having a fan-out structure.

Next, a modified example of the printed wiring board of this embodiment will be described. 4A to 4C are process sectional views showing an example of a manufacturing process of the printed wiring board 500. FIG. As shown in FIG. 4C, the printed wiring board 500 of the present modification is a printed wiring board that does not have a core layer.
The printed wiring board 500 of the present embodiment can be a coreless resin substrate that is not provided with a core layer having a fiber base material, and is constituted by, for example, a buildup layer or a solder resist layer. These build-up layers and solder resist layers are preferably composed of insulating layers formed of a cured product of the resin film of the present embodiment. For example, the printed wiring board 500 shown in FIG. 4C includes two build-up layers (insulating layers 540 and 550) and a solder resist layer (insulating layer 560). Note that the build-up layer of the printed wiring board 500 may be a single layer or may have two or more layers.

Since the insulating layer formed of the cured resin film of this embodiment is excellent in toughness, warpage of the printed wiring board 500 and cracks during transportation can be suppressed.

The metal layers 542, 552, and 562 shown in FIG. 4C may be circuit patterns, electrode pads, or may be formed by the SAP method as described above. . These metal layers 542, 552, and 562 may be a single layer or a plurality of metal layers.

The printed wiring board 500 may have a large area on which a plurality of semiconductor elements can be mounted on a plane. As a result, a plurality of semiconductor packages can be obtained by collectively sealing a plurality of semiconductor elements mounted on the printed wiring board 500 and then separating them into individual pieces. The printed wiring board 500 can be a panel board having a substantially circular shape or a rectangular shape.

The method for manufacturing the printed wiring board 500 is not particularly limited. For example, the printed wiring board 500 can be obtained by forming the buildup layer and the solder resist layer on the support substrate 510 and then peeling the support substrate 510. Specifically, as shown in FIG. 4A, a carrier foil 520 and a metal foil 530 (for example, copper foil) are arranged on a large-area support substrate 510 (for example, a plate member made of SUS). To do. At this time, an adhesive resin (not shown) can be provided between the support substrate 510 and the carrier foil 520. Subsequently, a metal layer 542 is formed on the metal foil 530. The metal layer 542 is patterned by a normal method such as an SAP method. Subsequently, after laminating the above resin film with a carrier film by a heating and pressing method or the like, the carrier substrate is peeled from the resin film with a carrier film. Then, the resin film is cured. These are repeated three times to form two build-up layers and one solder resist layer.
Thereafter, the support substrate 510 is peeled off as shown in FIG. Then, the metal foil 530 is removed by etching or the like.
Thus, the printed wiring board 500 shown in FIG. 4C is obtained.

Next, a modified example of the printed wiring board of this embodiment will be described. FIG. 5 is a cross-sectional view showing an example of the configuration of the printed wiring board 600.
A printed wiring board 600 shown in FIG. 5 may be composed of a coreless resin substrate 610 used in a PLP (panel level package) process. In the PLP process, for example, a panel size package having a larger area than a wafer can be obtained by using a wiring board process. By using the PLP process, the productivity of the semiconductor package can be improved more efficiently than the wafer level process.

In the present embodiment, the insulating layer 612 (interlayer insulating layer) and the insulating layers 630 and 632 (solder resist layer) of the coreless resin substrate 610 are configured by an insulating layer formed of a cured product of the resin film of the present embodiment. May be. Since the cured product of the resin film of this embodiment is excellent in toughness, it effectively suppresses warpage of the printed wiring board 600 and cracks of the coreless resin board 610 especially during transportation and mounting during the PLP process. be able to.

Further, the printed wiring board 600 of the present embodiment has a large area in which a plurality of semiconductor elements (not shown) can be mounted in the plane. Then, after sealing a plurality of semiconductor elements mounted in the in-plane direction of the printed wiring board 600 together, a plurality of semiconductor packages can be obtained by separating them into individual pieces. In this embodiment, since the linear expansion coefficient of the cured product of the resin film can be lowered, package warpage can be suppressed in the semiconductor package obtained by the PLP process.

The printed wiring board 600 can include a coreless resin substrate 610 and a solder resist layer (insulating layers 630 and 632) formed on the surface thereof. The coreless resin substrate 610 may have a built-in semiconductor element 620. The semiconductor element 620 can be electrically connected through the via wiring 616. The coreless resin substrate 610 can have at least an insulating layer 612 (interlayer insulating layer) and a via wiring 616. Via the via wiring 616, the lower metal layer 640 (electrode pad) and the upper metal layer 618 (post) can be electrically connected. Further, the via wiring 616 can be connected to the metal layer 640 via the metal layer 614 (post), for example. In the coreless resin substrate 610, a via wiring 616 and a metal layer 614 are embedded. The metal layer 614 that is a post may have a surface that is flush with the surface of the coreless resin substrate 610. In the printed wiring board 600 of the present embodiment, the coreless resin substrate 610 is configured by a single interlayer insulating layer, but is not limited to this configuration, and has a structure in which a plurality of interlayer insulating layers are stacked. May be. In such an interlayer insulating layer, at least a via wiring 616 may be formed as an interlayer connection wiring. In the present embodiment, the via wiring 616, the metal layer 614, or the metal layer 618 may be made of a metal such as copper, for example.

Further, the upper and lower surfaces of the coreless resin substrate 610 may be covered with a solder resist layer (insulating layers 630 and 632). For example, the insulating layer 630 can cover the metal layer 650 formed on the surface of the insulating layer 612. The metal layer 650 includes a first metal layer 652 (plating layer) and a second metal layer 654 (electroless plating layer), and may be a metal layer formed by the SAP method, for example. The metal layer 650 may be, for example, a circuit pattern or an electrode pad.

Moreover, the manufacturing method of the printed wiring board 600 of this embodiment is not specifically limited, For example, the following methods can be used. For example, the insulating layer 612 is formed over the supporting substrate. Subsequently, a via is formed in the insulating layer 612, and a via wiring 616 in which a metal film is embedded in the via by a plating method is formed. Subsequently, a rewiring (metal layer 650) is formed on the surface of the insulating layer 612 by the SAP method. Thereafter, a plurality of interlayer insulating layers having such interlayer connection wirings may be stacked. Thereafter, solder resist layers (insulating layers 630 and 632) are formed.
As described above, the printed wiring board 600 can be obtained.

Next, a modified example of the printed wiring board of this embodiment will be described. FIG. 6 is a cross-sectional view showing an example of the configuration of the printed wiring board 700.
A printed wiring board 700 shown in FIG. 6 can be formed of a substrate with a post (MIS substrate). For example, the post-attached substrate can be constituted by a coreless resin substrate 710 having a structure in which a via wiring 716 and a metal layer 718 (post) are embedded in an insulating layer 712 (interlayer insulating layer). The post-attached substrate may be a substrate after being singulated or a substrate having a large area before being singulated (for example, a support like a wafer).
By using the printed wiring board 700 of the present embodiment, the productivity of the semiconductor package can be efficiently improved to the same level as or higher than that of the wafer level process.

In the present embodiment, the insulating layer 712 (interlayer insulating layer) and the insulating layers 730 and 732 (solder resist layer) of the coreless resin substrate 710 are configured by insulating layers formed of a cured product of the resin film of the present embodiment. May be. Since the cured product of the resin film of this embodiment is excellent in toughness, it is possible to effectively suppress warpage of the printed wiring board 700 and particularly cracks of the coreless resin substrate 710 during transportation and mounting.

In addition, the printed wiring board 700 of the present embodiment has a large area in which a plurality of semiconductor elements (not shown) can be mounted in the plane. Then, after sealing a plurality of semiconductor elements mounted in the in-plane direction of the printed wiring board 700 together, a plurality of semiconductor packages can be obtained by separating them into individual pieces. Since the linear expansion coefficient of the cured product of the resin film of this embodiment can be lowered, package warpage can be suppressed in the obtained semiconductor package.

The printed wiring board 700 can include a coreless resin substrate 710 and a solder resist layer (insulating layers 730 and 732) formed on the surface thereof. The coreless resin substrate 710 may have a built-in semiconductor element 720. The semiconductor element 720 can be electrically connected through the via wiring 716. The coreless resin substrate 710 can include at least an insulating layer 712 (interlayer insulating layer), a via wiring 716, and a metal layer 718 (post). The metal layer 714 (post) on the lower surface and the metal layer 718 (post) on the upper surface can be electrically connected via the via wiring 716. The metal layer 714 embedded in the insulating layer 712 can be connected to a metal layer 740 (electrode pad) formed on the surface of the insulating layer 712. Further, the surface of the insulating layer 712 may have a polished surface. One surface of the metal layer 718 may be flush with the polished surface of the insulating layer 712.

In the printed wiring board 700 of the present embodiment, the coreless resin substrate 710 is configured by a single interlayer insulating layer, but is not limited to this configuration, and has a structure in which a plurality of interlayer insulating layers are stacked. May be. In such an interlayer insulating layer, a via wiring 716 and a metal layer 718 (post) may be formed as an interlayer connection wiring. In the present embodiment, the via wiring 716, the metal layer 714, or the metal layer 718 may be made of a metal such as copper, for example. The upper and lower surfaces of the coreless resin substrate 710 may be covered with a solder resist layer (insulating layers 730 and 732).

Moreover, the manufacturing method of the printed wiring board 700 of this embodiment is not specifically limited, For example, the following methods can be used. For example, a copper post (eg, a metal layer 718) is formed over the insulating layer over the support substrate. A copper post is further embedded with an insulating layer. Subsequently, the surface of the copper post is exposed by a method such as grinding or chemical etching (that is, cueing of the copper post is performed). Subsequently, rewiring is formed by the SAP method. Through such a process, the coreless resin substrate 710 having an interlayer insulating layer can be formed. Thereafter, a plurality of interlayer insulating layers having interlayer connection wirings may be stacked by repeating the step of forming the interlayer insulating layer a plurality of times. Thereafter, solder resist layers (insulating layers 730 and 732) are formed.
Thus, the printed wiring board 700 can be obtained.

As described above, the embodiments of the present invention have been described with reference to the drawings. However, these are exemplifications of the present invention, and various configurations other than the above can be adopted.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the description of these examples.

(Preparation of thermosetting resin composition)
About the Example and the comparative example, the varnish-like thermosetting resin composition was prepared.
First, each component was dissolved or dispersed at a solid content ratio shown in Table 1, and the resin varnish was prepared by stirring with a high-speed stirring device so that the nonvolatile content was 70% by weight with methyl ethyl ketone.
In addition, the numerical value which shows the mixture ratio of each component in Table 1 has shown the mixture ratio (weight%) of each component with respect to the whole solid content of a thermosetting resin composition.

Details of each component in Table 1 are as follows.
In the examples and comparative examples, the following raw materials were used.
(Thermosetting resin)
Thermosetting resin 1: fluorene type epoxy resin (EG-280, manufactured by Osaka Gas Chemical Co., Ltd., liquid at 25 ° C., viscosity 6 Pa · s, epoxy equivalent 460 g / eq)
Thermosetting resin 2: bisphenol A type epoxy resin (EXA-4850-150, manufactured by DIC, liquid at 25 ° C., viscosity 15 Pa · s, epoxy equivalent 450 g / eq)
Thermosetting resin 3: polyether type epoxy resin (AER-9000, manufactured by Asahi Kasei Corporation, liquid at 25 ° C., viscosity 1 Pa · s, epoxy equivalent 380 g / eq)
Thermosetting resin 4: Bisphenol F type epoxy resin (EPICLON, 830S, manufactured by DIC, viscosity 3.8 Pa · s, epoxy equivalent 171 g / eq)
Thermosetting resin 5: Bismaleimide (BMI-1500, manufactured by Designa Molecules Co., Ltd., viscosity 40 Pa · s, weight average molecular weight (Mw) 1500)
Thermosetting resin 6: naphthylene ether type epoxy resin (HP-6000, manufactured by DIC, epoxy equivalent 250 g / eq)
The viscosity of the thermosetting resin was measured using an E-type viscometer at room temperature of 25 ° C.
(Benzoxazine compound)
Benzoxazine compound 1: benzoxazine compound represented by the following formula (Pd-type benzoxazine manufactured by Shikoku Chemicals)

(Phenoxy resin)
Phenoxy resin 1: Phenoxy resin (YX6954, manufactured by Mitsubishi Chemical Corporation, Mw: 40,000)
Phenoxy resin 2: Phenoxy resin (YX6900, manufactured by Mitsubishi Chemical Corporation, Mw: 15,000)
(Other)
(Meth) acrylic acid ester polymer 1: PMS-13-7, manufactured by Nagase ChemteX Corporation, Mw: 10 × 104, epoxy-modified acrylic resin, Tg = 17 ° C., epoxy value = 0.20 eq / kg)
(Curing agent)
Curing agent 1: phenolic curing agent (phenol novolac resin, HF-3, manufactured by Sumitomo Bakelite Co., Ltd.)
Curing agent 2: Phenolic curing agent (manufactured by Nippon Kayaku Co., Ltd., GPH-103)
Curing agent 3: Amine-based curing agent (diethyltoluenediamine, manufactured by Mitsui Chemicals Fine, DETDA)
Curing agent 4: Catalyst-type curing agent / imidazole compound (Shikoku Kasei Kogyo Co., Ltd., Curazole 1B2PZ)
(Inorganic filler)
Inorganic filler 1: spherical silica (SO-C4 manufactured by Admatechs, average particle size 1.0 μm, phenylaminosilane treatment)
(Coupling agent)
Coupling agent 1: Silane coupling agent (N-phenyl γ-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical, KBM-573)

(Resin film with carrier)
In Examples and Comparative Examples, the obtained resin varnish was applied on a PET film as a carrier substrate, and then the solvent was removed at 120 ° C. for 5 minutes to form a resin film having a thickness of 25 μm. Thereby, a resin film with a carrier was obtained.

(Manufacture of semiconductor packages)
1. Manufacture of printed wiring board First, double-sided copper-clad laminate (Sumitomo Bakelite Co., Ltd., LAZ-4785TH-G) using ultra-thin copper foil (Mitsui Metal Mining Co., Ltd., Micro Thin Ex, 2.0 μm). Thickness 0.2 mm) was prepared. Next, the ultrathin copper foil layer on the surface of the double-sided copper clad laminate was subjected to a roughening treatment of about 1 μm, and then a through hole of φ80 μm for interlayer connection was formed with a carbon dioxide gas laser. Next, the double-sided copper-clad laminate with through-holes formed was immersed in a 60 ° C. swelling liquid (Atotech Japan Co., Ltd., Swelling Dip Securigant P) for 5 minutes, and then an 80 ° C. potassium permanganate aqueous solution (Atotech Japan). After immersion in Concentrate Compact CP) for 2 minutes, neutralization and desmear treatment in the through hole was performed. Next, electroless copper plating is performed on the double-sided copper clad laminate after desmearing treatment to a thickness of 0.5 μm, a resist layer for electrolytic copper plating is formed to a thickness of 18 μm, and pattern copper plating is performed. The film was post-cured by heating at 150 ° C. for 30 minutes. Next, the plating resist was peeled off and the entire surface was flash-etched to form circuit patterns on both sides with L / S = 15/15 μm.
The two-stage vacuum pressurization method is performed after laminating the resin film with carrier obtained above (as an interlayer insulating film) on both sides so that the resin film faces the circuit pattern on the circuit board after the circuit pattern is formed. Using a laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.), decompressed for 30 seconds, 10 hPa or less, temperature 120 ° C., pressure 0.8 MPa, 30 seconds as one stage condition, temperature with SUS end plate as two stage condition Vacuum heating and pressure molding was performed at 120 ° C. and a pressure of 1.0 MPa for 60 seconds. Subsequently, after peeling off the carrier substrate from the resin film with carrier, the resin film on the circuit pattern was cured at 200 ° C. for 2 hours. Next, circuit processing was performed by a semi-additive method, and the resin film with carrier obtained above (as a solder resist layer) was similarly laminated on both sides, and laser-opened to obtain a printed wiring board.

2. Manufacturing of Semiconductor Device A 10 mm × 10 mm × 100 μm thick semiconductor element with solder bumps is mounted on the obtained printed wiring board, and sealed with an underfill (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4160G) at 150 ° C. Cured for 2 hours. Finally, dicing was performed to 15 mm × 15 mm to obtain a semiconductor device.

In the examples and comparative examples, the following evaluation was performed. The evaluation results are shown in Table 2.

(Cured product)
Four resin films from which the PET film, which is a carrier base material, was peeled from the obtained resin film with carrier were laminated to prepare a resin sheet having a thickness of 100 μm. Next, the resin sheet was heat-treated at 200 ° C. for 2 hours to obtain a cured product of the thermosetting resin composition.

(Storage modulus)
(2) Storage elastic modulus E '
The storage elastic modulus E ′ was measured using a dynamic viscoelasticity measuring device (DMA device, manufactured by TA Instruments, Q800).
A test piece of 8 mm × 40 mm was cut out from the obtained cured product. With respect to the cut out test piece, the storage elastic modulus at 30 ° C. was measured at a heating rate of 5 ° C./min and a frequency of 1 Hz, and the storage elastic modulus E ′ ₃₀ at 30 ° C. was calculated.

(Tensile elongation)
The obtained cured product was cut into a test piece having a length of 100 mm and a width of 6 mm. In the tensile test, the test piece was sandwiched between chucks arranged at a constant distance, and evaluation was performed by pulling at a constant speed until the test piece broke. At this time, using a precision universal testing machine (manufactured by Shimadzu Corp., Autograph AG-IS), initial chuck distance L: 20 mm, test piece thickness: 0.1 mm, measurement temperature: 25 ° C., test speed: 1 mm The conditions per minute were used. In the tensile test, the tensile elongation rate (%) was calculated from the amount of displacement when fractured under the above conditions and the initial inter-chuck distance.

(Average linear expansion coefficient (50 ° C to 250 ° C))
A test piece of 4 mm × 40 mm was cut out from the obtained cured product. Using the thermomechanical analyzer TMA (TA Instrument Co., Ltd., Q400) for the cut out test piece, under the conditions of a temperature range of 50 to 250 ° C., a heating rate of 10 ° C./min, a load of 10 g, and a tensile mode. Thermomechanical analysis (TMA) was measured for 2 cycles. The average value of the linear expansion coefficient in the plane direction (XY direction) in the range of 50 ° C. to 250 ° C. was calculated. In addition, the value of the 2nd cycle was employ | adopted for the linear expansion coefficient.

(Glass transition temperature, loss tangent tan δ)
A test piece of 8 mm × 40 mm was cut out from the obtained cured product. Dynamic viscoelasticity measurement was performed on the cut out test piece at a temperature rising rate of 5 ° C./min and a frequency of 1 Hz. The glass transition temperature and loss tangent tan δ were measured by dynamic viscoelasticity measurement (DMA device, manufactured by TA Instruments, Q800). Here, the glass transition temperature was a temperature at which the loss tangent tan δ showed the maximum value. Further, the half value width was calculated from the peak value of the obtained loss tangent tan δ.

(Bending test)
The obtained cured product was used as a sample test plate. The sample thickness of the sample test plate was 100 μm. This sample test plate was bent at 180 ° C. along a support rod having a predetermined diameter, and the presence or absence of breakage was evaluated. Then, the diameter was gradually reduced, and the minimum diameter that did not break was defined as the minimum diameter shown in Table 2. However, the smallest diameter that can be evaluated is 2 mm.

(Panel warpage)
A 12 μm copper foil is placed on a support substrate of length 250 mm × width 250 mm square SUS, and a resin film with a carrier film obtained in Examples and Comparative Examples is a two-stage vacuum / pressure laminator (manufactured by Meiki Seisakusho, MVLP-500), decompressed for 30 seconds, 10 hPa or less, temperature 120 ° C., pressure 0.8 MPa, 30 seconds as 1 stage condition, temperature 120 ° C., pressure 1.0 MPa, 60 with 2 stage conditions as SUS end plate Vacuum heating and pressure forming was performed in seconds. Next, the carrier substrate was peeled from the resin film with carrier, and then cured at 180 ° C. for 2 hours. This was repeated three times to form a three-layer build-up layer, and panel warpage when SUS was peeled was evaluated. The warpage of the plate edge was measured.
A: Less than 15 mm B: 15 mm or more and less than 50 mm (substantially no problem)
C: 50 mm or more

(Handling properties)
After the SUS peeling, a 12 μm copper foil was further etched. Thereafter, the presence or absence of cracks in the panel was evaluated.
A: No crack B: Crack

It was found that the insulating layers formed of the thermosetting resin compositions of Examples 1 to 8 showed excellent results with respect to panel warpage and handling properties and were excellent in toughness. On the other hand, the insulating layers formed of the thermosetting resin compositions of Comparative Examples 1 to 4 did not have sufficient toughness. In addition, from the evaluation result of Comparative Example 3, even when the tensile elongation percentage of the cured product of the thermosetting resin composition is 2% or more, when the storage elastic modulus E ′ of the cured product is larger than 10 GPa, the panel It turned out that curvature became large and it did not have sufficient toughness. Further, from the evaluation results of Comparative Example 4, even when the storage elastic modulus E ′ of the cured product of the thermosetting resin composition is 1 GPa or more and 10 GPa or less, the panel warpage is also caused when the tensile elongation is less than 2%. It was found to be large and does not have sufficient toughness.

As described above, the present invention has been described more specifically based on the embodiments. However, these are exemplifications of the present invention, and various configurations other than the above can be adopted.

The thermosetting resin composition of the present invention includes a thermosetting resin, a curing agent, and an inorganic filler. The cured product has a storage elastic modulus E ′ ₃₀ at 30 ° C. and a tensile elongation of the cured product. The rate is within the predetermined range described above. The insulating film formed using the thermosetting resin composition of the present invention having such characteristics exhibits excellent toughness by achieving both low elasticity and high elongation. Therefore, because it is excellent in toughness when used in such an insulating layer, warpage of the panel (coreless substrate) and substrate cracks during transportation and mounting during the panel level process of manufacturing a large panel size package. Can be suppressed. Therefore, the present invention has industrial applicability.

Claims

A thermosetting resin composition used for forming an insulating layer in a printed wiring board,
A thermosetting resin;
A curing agent;
An inorganic filler,
When subjected to dynamic viscoelasticity measurement with respect to the cured product of the thermosetting resin composition, the storage modulus E '30 at 30 ° C. of the cured product is less 10GPa least 1 GPa,
A thermosetting resin composition, wherein a tensile elongation rate of the cured product is 2% or more when a tensile test is performed on the cured product.
The thermosetting resin composition according to claim 1, wherein the content of the inorganic filler is 65% by weight or more and 90% by weight or less with respect to the entire thermosetting resin composition.
When dynamic viscoelasticity measurement is performed on the cured product under conditions of a temperature rising rate of 5 ° C./min and a frequency of 1 Hz, the peak value of the loss tangent tan δ of the cured product is 0.25 or more and 1 or less. The thermosetting resin composition according to claim 1 or 2.
The thermosetting resin composition according to claim 3, wherein a half value width of a peak value of the loss tangent tan δ is in a range of 20 or more and 100 or less.
The average linear expansion coefficient calculated in the range of 50 ° C to 250 ° C of the cured product when a thermomechanical analysis is performed on the cured product is 1 ppm / ° C or more and 120 ppm / ° C or less. The thermosetting resin composition according to any one of the above.
The thermosetting resin composition according to any one of claims 1 to 5, wherein the thermosetting resin composition has a viscosity at 25 ° C of 0.1 Pa · s to 200 Pa · s.
The thermosetting resin composition according to any one of claims 1 to 6, wherein the thermosetting resin contains an epoxy resin.
The thermosetting resin composition according to any one of claims 1 to 7, further comprising a phenoxy resin having a weight average molecular weight of 10,000 to 60,000.
The thermosetting resin composition according to any one of claims 1 to 8, wherein the inorganic filler has an average particle diameter of 0.5 µm to 2 µm.
The thermosetting resin composition according to any one of claims 1 to 9, wherein the inorganic filler contains silica.
The thermosetting resin composition according to any one of claims 1 to 10, wherein a glass transition temperature of the cured product is 10 ° C or higher and 220 ° C or lower.
The thermosetting resin composition according to any one of claims 1 to 11, wherein the printed wiring board does not contain glass fiber.
A carrier substrate;
A resin film with a carrier, comprising: a resin film provided on the carrier base material and formed with the thermosetting resin composition according to any one of claims 1 to 12.
A printed wiring board comprising an insulating layer composed of a cured product of the thermosetting resin composition according to any one of claims 1 to 12.
A printed wiring board according to claim 14,
A semiconductor device comprising: a semiconductor element mounted on a circuit layer of the printed wiring board or built in the printed wiring board.