JP2020136311A - Resin composition, resin film with carrier using the same, pre-preg, laminate sheet, printed wiring board and semiconductor device - Google Patents

Abstract

To provide a resin composition with excellent low dielectric characteristic and metal adhesiveness.SOLUTION: The resin composition is a resin composition for circuit board and includes an allyl compound with an alicyclic structure in a molecule, a maleimide compound, polymerization initiator and an inorganic filler.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin composition, a resin film with a carrier using the resin composition, a prepreg, a laminated board, a printed wiring board, and a semiconductor device.

So far, various developments have been made in resin compositions used for electrical and electronic members. As this kind of technique, for example, the technique described in Patent Document 1 is known. Patent Document 1 describes a thermosetting resin composition for the electric and electronic industries containing an allylphenol type phenol resin and a bismaleimide compound (Table 1 of Patent Document 1).

Japanese Unexamined Patent Publication No. 2017-43767

However, as a result of the examination by the present inventor, it has been found that the resin composition described in Patent Document 1 has room for improvement in terms of low dielectric property and metal adhesion.

As a result of further studies, the present inventor has further investigated and found that by using a resin composition containing an allyl compound and a maleimide compound having an alicyclic structure in the molecule, the low dielectric property and metal adhesion in the resin film are improved. Has been completed.

According to the present invention
A resin composition for circuit boards
An allyl compound having an alicyclic structure in the molecule,
Maleimide compound and
Polymerization initiator and
A resin composition comprising, and an inorganic filler, is provided.

Further, according to the present invention.
Carrier base material and
A resin film made of the above resin composition provided on the carrier base material and
A resin film with a carrier is provided.

Further, according to the present invention, there is provided a prepreg containing a fiber base material in the above resin composition.

Further, according to the present invention, there is provided a laminated plate in which a metal layer is arranged on at least one surface of the prepreg.

Further, according to the present invention, there is provided a printed wiring board provided with an insulating layer made of a cured product of the above resin composition.

Further, according to the present invention.
With the above printed wiring board
Provided is a semiconductor device including 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, there is provided a resin composition having low dielectric properties and excellent metal adhesion, a resin film with a carrier using the resin composition, a prepreg, a laminated board, a printed wiring board, and a semiconductor device.

It is a figure which shows typically an example of the structure of the resin sheet with a base material which concerns on this embodiment. It is a process sectional view which shows an example of the manufacturing process of the semiconductor device which concerns on this embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by the same reference numerals, and description thereof will be omitted as appropriate. Moreover, the figure is a schematic view and does not match the actual dimensional ratio.

The resin composition of the present embodiment is a resin composition for a circuit board, and contains an allyl compound having an alicyclic structure in the molecule, a maleimide compound, a polymerization initiator, and an inorganic filler.

According to the findings of the present inventor, by using a resin composition containing an allyl compound and a maleimide compound having an alicyclic structure in the molecule, the low dielectric property and metal adhesion in the resin film are improved. Although the detailed mechanism is not clear, maleimide compounds and compounds containing alicyclic structures are materials with a relatively low dielectric constant, have good compatibility with allyl compounds and maleimide compounds, and have an alicyclic in the molecule of the allyl compound. It is considered that the metal adhesion can be improved because a resin film that is soft and has excellent toughness can be realized by the formula structure.

Further, according to the resin composition of the present embodiment, a build-up layer that can be optimally used in the SAP method can be realized, and the low dielectric loss tangent of the build-up layer and the SAP characteristics can be compatible with each other.
In the present embodiment, the SAP characteristics indicate that the surface roughness of the circuit layer after the desmear treatment is small and that the plating adhesion between the build-up layer and the circuit layer is high. By improving the SAP characteristics, a high-density circuit can be formed and the connection reliability can be improved. Further, since the build-up layer made of the resin composition of the present embodiment can reduce the dielectric loss tangent, it is possible to realize a low transmission loss.

In the present embodiment, examples of the insulating layer in the printed wiring board include insulating members constituting the printed wiring board such as a core layer, a build-up layer (interlayer insulating layer), and a solder resist layer. Among these, the cured product of the resin composition of the present embodiment is used for the build-up layer.

The printed wiring board includes a core layer, a build-up layer (interlayer insulation layer), a printed wiring board having a solder resist layer, a printed wiring board having no core layer, and a coreless board used in a panel package process (PLP). , MIS (Molded Infect Substrate) substrate and the like.

The cured product of the resin film made of the resin composition of the present embodiment is used for the build-up layer. For example, a build-up layer in a printed wiring board having no core layer and a coreless substrate used for PLP are built. It can also be used as an up layer, a build-up layer of a MIS substrate, and the like. As described above, the cured product of the resin film of the present embodiment also serves as a build-up layer constituting the printed wiring board in a large-area printed wiring board used for collectively producing a plurality of semiconductor packages. It can be preferably used. It can also be applied to the build-up layer that constitutes the printed wiring board in a system to which a large-scale current is supplied.

Hereinafter, each component of the resin composition of the present embodiment will be described in detail.

(Allyl compound)
The resin composition contains an allyl compound having an alicyclic structure in the molecule.
An allyl compound having an alicyclic structure in the molecule may have an aromatic ring in the molecule, and has an aromatic-containing structure in which aromatic rings such as a benzene ring are linked via a methylene group. You may. One or two or more aromatic-containing structures may be contained in the molecule. The allyl compound may have an alicyclic structure having a structure arranged between the aromatic-containing structures.

The allyl group in the allyl compound may be located inside or at the end of the molecule, and may contain one or two or more. As an example, the allyl group may be attached directly to the aromatic ring, or may be attached via a linking group. Examples of the linking group include an oxygen atom and the like.

As the allyl compound having an alicyclic structure in the molecule, for example, a compound represented by the following general formula Aly1 or general formula Aly2 may be contained.

In the general formula Aly1 and the general formula Aly2, X and Z are divalent hydrocarbon groups having 1 to 12 carbon atoms, or a aliphatic or aromatic group containing a polar group, and aryl groups and Y are alicyclic groups. It is a group having a structure. n represents an integer of 1 to 10. The alicyclic structure may be monocyclic, bicyclic, or polycyclic, and the number of carbon atoms thereof may be, for example, 3 to 20 or 3 to 15.

Examples of the allyl compound having an alicyclic structure in the molecule include FTC809AE and FATC809 manufactured by Gun Ei Chemical Industry Co., Ltd.

The weight average molecular weight of the allyl compound is, for example, 1,000 to 5,000, preferably 1,200 to 4,000, and particularly preferably 1,500 to 3,000. Although the detailed mechanism is not clear, it is considered that the dielectric loss tangent can be lowered because the molecular weight between the cross-linking points becomes large and the polarity becomes low by using the one having a relatively large molecular weight.

The lower limit of the content of the allyl compound is not particularly limited, but for example, when the total solid content of the resin composition (that is, the component excluding the solvent) is 100% by mass, it may be 1% by mass or more and 2% by mass. % Or more, or 3% by mass or more. As a result, low polarity, high conductor adhesion, low dielectric constant, and low dielectric loss tangent can be achieved. The upper limit of the content of the allyl compound is not particularly limited. For example, when the total solid content of the thermosetting resin composition is 100% by mass, it may be 50% by mass or less, or 25% by mass or less. It may be 20% by mass or less. This allows for low coefficient of thermal expansion and heat resistance.

In the present embodiment, the solid content of the resin composition refers to the non-volatile content in the resin composition, and refers to the balance excluding volatile components such as water and solvent. The content of the resin composition with respect to the total solid content means the content of the resin composition with respect to the total solid content (100% by mass) excluding the solvent when the solvent is contained.

(Maleimide compound)
The resin composition of the present embodiment can contain a maleimide compound.
In the present embodiment, the maleimide group of the maleimide compound has a five-membered ring planar structure, and the double bond of the maleimide group easily interacts between the molecules and has high polarity. Therefore, the maleimide group, the benzene ring, and other planar surfaces. It exhibits strong intermolecular interaction with compounds having a structure and can suppress molecular motion. Therefore, by containing the maleimide compound in the resin composition, the coefficient of linear expansion of the obtained insulating layer can be lowered, the glass transition temperature can be improved, and the heat resistance can be further improved.

As the maleimide compound, a maleimide compound having at least two maleimide groups in the molecule is preferable.
Examples of maleimide compounds having at least two maleimide groups in the molecule include 4,4'-diphenylmethanebismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, and 2,2-bis [4- (4-maleimide). Phenoxy) phenyl] propane, bis- (3-ethyl-5-methyl-4-maleimidephenyl) methane, 4-methyl-1,3-phenylenebismaleimide, N, N'-ethylenedimaleimide, N, N'- Hexamethylene dimaleimide, bis (4-maleimidephenyl) ether, bis (4-maleimidephenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, etc. Examples thereof include compounds having two maleimide groups in the molecule, compounds having three or more maleimide groups in the molecule such as polyphenylmethane maleimide, and the like.
One of these types can be used alone, or two or more types can be used in combination. Among these maleimide compounds, 4,4'-diphenylmethane bismaleimide, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane, and bis- (3-ethyl-) are considered to have low water absorption. 5-Methyl-4-maleimidephenyl) methane, polyphenylmethane maleimide, bisphenol A diphenyl ether bismaleimide are preferred.

The maleimide compound preferably contains a maleimide compound represented by the following formula (1).

（上記式（１）において、ｎ_１は０以上１０以下の整数であり、Ｘ_１はそれぞれ独立に炭素数１以上１０以下のアルキレン基、下記式（１ａ）で表される基、式「−ＳＯ_２−」で表される基、「−ＣＯ−」で表される基、酸素原子または単結合であり、Ｒ_１はそれぞれ独立に炭素数１以上６以下の炭化水素基であり、ａはそれぞれ独立に０以上４以下の整数であり、ｂはそれぞれ独立に０以上３以下の整数である）

(In the above formula (1), n ₁ is an integer of 0 or more and 10 or less, and X ₁ is an alkylene group having 1 or more and 10 or less carbon atoms independently, a group represented by the following formula (1a), and the formula "-". A group represented by "SO _2- ", a group represented by "-CO-", an oxygen atom or a single bond, R ₁ is an independently hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms, and a is Each is an integer of 0 or more and 4 or less independently, and b is an integer of 0 or more and 3 or less independently.)

（上記式（１ａ）において、Ｙは芳香族環を有する炭素数６以上３０以下の炭化水素基であり、ｎ_２は０以上の整数である）

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

The alkylene group of 1 or more and 10 or less in X ₁ is not particularly limited, but a linear or branched alkylene group is preferable.

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 and tetramethylene group. Groups, pentamethylene groups, hexamethylene groups and the like can be mentioned.

Specific examples of the branched alkylene group include -C (CH ₃ ) _2- (isopropylene group), -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C. Alkylmethyl 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 -CH ₂ - such as an alkyl ethylene group such as and the like.

The carbon number of the alkylene group in X ₁ may be 1 or more and 10 or less, but is preferably 1 or more and 7 or less, and more 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.

Further, R ₁ is independently a hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms, but it is preferably a hydrocarbon group having 1 or 2 carbon atoms, specifically, a methyl group or an ethyl group. ..

Further, a is an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 2 or less, and more preferably 0. Further, b is an integer of 0 or more and 3 or less, preferably 0 or 1, and more preferably 0.

Further, n ₁ is an integer of 0 or more and 10 or less, preferably an integer of 0 or more and 6 or less, more preferably an integer of 0 or more and 4 or less, and particularly preferably an integer of 0 or more and 3 or less. preferable. Also, the maleimide compound is more preferably n ₁ in formula (1) contains at least one or more compounds. As a result, the insulating layer obtained from the resin composition exhibits more excellent heat resistance.
Further, in the above formula (1a), Y is a hydrocarbon group having an aromatic ring and having 6 or more and 30 or less carbon atoms, and n ₂ is an integer of 0 or more.

The hydrocarbon group having 6 to 30 carbon atoms having the aromatic ring may be composed of only the aromatic ring, or may have a hydrocarbon group other than the aromatic ring. The aromatic ring of Y may be one, two or more, and when two or more, these aromatic rings may be the same or different. Further, the aromatic ring may have either a monocyclic structure or a polycyclic structure.

Specifically, examples of the hydrocarbon group having an aromatic ring and having 6 or more and 30 or less carbon atoms include fragrances such as benzene, biphenyl, naphthalene, anthracene, fluorene, phenalene train, indecene, terphenyl, acenaphthylene and phenalene. Examples thereof include a divalent group obtained by removing two hydrogen atoms from the nucleus of a compound having a group property.

Moreover, these aromatic hydrocarbon groups may have a substituent. Here, the term that the aromatic hydrocarbon group has a substituent means that a part or all of the hydrogen atoms constituting the aromatic hydrocarbon group are substituted with the substituent. Examples of the substituent include an alkyl group.

The alkyl group as the substituent is preferably a chain alkyl group. Further, the carbon number thereof 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 thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a sec-butyl group and the like.

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

上記式（１ａ−１）、（１ａ−２）中、Ｒ_４は、それぞれ独立に炭素数１以上６以下の炭化水素基である。ｅはそれぞれ独立に０以上４以下の整数、より好ましくは０である。

The formula (1a-1), in (1a-2), _{R 4} are each independently 1 or 6 carbon atoms or less hydrocarbon groups. e is an integer of 0 or more and 4 or less, more preferably 0, respectively.

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

From the above, in the maleimide compound represented by the above formula (1), X ₁ is a linear or branched alkylene group having 1 or more and 3 or less carbon atoms, and a hydrocarbon having R ₁ of 1 or 2 is used. It is preferable that a is an integer of 0 or more and 2 or less, b is 0 or 1, and n ₁ is an integer of 1 or more and 4 or less. Alternatively, X ₁ is a group represented by any of the above formulas (1a-1) and (1a-2), and e is preferably 0. As a result, the insulating layer obtained from the resin composition exhibits more excellent low heat shrinkage and chemical resistance.

As a preferable specific example of the maleimide compound represented by the above formula (1), for example, the maleimide compound represented by the following formula (1-1) is particularly preferably used.

Further, the maleimide compound may contain a maleimide compound of a type different from the maleimide compound represented by the above formula (1).
Examples of such maleimide compounds include 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, hexamethylenediamine bismaleimide, N, N'-1,2-ethylene bismaleimide, N, N'. An aliphatic maleimide compound such as -1,3-propylene bismaleimide, N, N'-1,4-tetramethylene bismaleimide; and an imide-extended bismaleimide can be mentioned. Of these, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane and imide-extended bismaleimide are particularly preferable. The maleimide compound may be used alone or in combination of two or more.
Examples of the imide-extended bismaleimide include a maleimide compound represented by the following formula (a1), a maleimide compound represented by the following formula (a2), and a maleimide compound represented by the following formula (a3). Specific examples of the maleimide compound represented by the formula (a1) include BMI-1500 (manufactured by Digigner Moleculars, molecular weight 1500) and the like. Specific examples of the maleimide compound represented by the formula (a2) include BMI-1700 (manufactured by Digigner Moleculars, molecular weight 1700), BMI-1400 (manufactured by Digigner Moleculars, molecular weight 1400) and the like. Specific examples of the maleimide compound represented by the formula (a3) include BMI-3000 (manufactured by Digigner Moleculars, molecular weight 3000) and the like.

上記式（ａ１）において、ｎは１以上１０以下の整数を示す。

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

上記式（ａ２）において、ｎは１以上１０以下の整数を示す。

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

上記式（ａ３）において、ｎは１以上１０以下の整数を示す。

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 Mw400 or more, and particularly preferably Mw800 or more. When Mw is at least the above lower limit value, it is possible to suppress the occurrence of tackiness in the insulating layer. The upper limit of Mw is not particularly limited, but is preferably Mw4000 or less, and more preferably Mw2500 or less. When Mw is not more than the above upper limit value, the handleability is improved at the time of producing the insulating layer, and it becomes easy to form the insulating layer. The Mw of the maleimide compound can be measured by, for example, GPC (gel permeation chromatography, standard substance: polystyrene conversion).

Further, as the maleimide compound, a reaction product of the maleimide compound and the amine compound can also be used. As the amine compound, at least one selected from aromatic diamine compounds and monoamine compounds can be used.

Examples of the aromatic diamine compound include o-dianicidin, o-trizine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 2,2'. -Dimethyl-4,4'-diaminobiphenyl, 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-phenylenediisopropyridene) dianiline, 2,2- [4- (4) -Aminophenoxy) phenyl] propane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, bis (4- (4-aminophenoxy) phenyl) sulfone and the like.

Examples of the monoamine compound include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, and m-amino. Benzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, o-aniline, m-aniline, p-aniline, o-methylaniline, m-methylaniline, p- Methylaniline, o-ethylaniline, m-ethylaniline, p-ethylaniline, o-vinylaniline, m-vinylaniline, p-vinylaniline, o-allylaniline, m-allylaniline, p-allylaniline and the like. Be done.

The reaction between the maleimide compound and the amine compound can be carried out in an organic solvent. The reaction temperature is, for example, 70 to 200 ° C., and the reaction time is, for example, 0.1 to 10 hours.

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

(Polymerization initiator)
The resin composition contains a polymerization initiator.
As the polymerization initiator, a polymerization initiator that initiates polymerization by light and / or heating can be used, and among these, a radical polymerization initiator is preferable.

Peroxide may be used as the above-mentioned polymerization initiator, and specifically, for example, azobisisobutyronitrile, isobutylyl peroxide, diisopropylperoxydicarbonate, t-hexylperoxy-2-ethyl. Organic peroxides such as hexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dicumyl peroxide, t-butylcumyl peroxide, t-butyl hydroperoxide, etc. Can be mentioned. These may be used alone or in combination of two or more.

The content of the polymerization initiator is not particularly limited, but is preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the allyl compound.

(Inorganic filler)
The resin composition contains an inorganic filler.
Examples of the inorganic filler include silicates such as talc, fired clay, unburned clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, silica, and molten silica; calcium carbonate, magnesium carbonate, and hydro. Carbonates such as tarcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide; sulfates or sulfates such as barium sulfate, calcium sulfate, calcium sulfite; zinc borate, barium metaborate, boric acid Borates such as aluminum, calcium borate, sodium borate; nitrides such as aluminum hydroxide, boron nitride, silicon nitride, carbon nitride; titanates such as strontium titanate and barium titanate can be mentioned.
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 of them may be used in combination.

The lower limit of the average particle size of the inorganic filler is not particularly limited, but may be, for example, 0.01 μm or more, or 0.05 μm or more. As a result, it is possible to suppress an increase in the viscosity of the varnish of the thermosetting resin, and it is possible to improve workability at the time of producing the insulating layer. The upper limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 5.0 μm or less, more preferably 2.0 μm or less, still more preferably 1.0 μm or less. As a result, phenomena such as sedimentation of the inorganic filler in the varnish of the thermosetting resin can be suppressed, and a more uniform resin film can be obtained. Further, when the circuit dimension L / S of the printed wiring board is less than 20 μm / 20 μm, the influence on the insulation between the wirings can be suppressed.

In the present embodiment, the average particle size of the inorganic filler is measured by measuring the particle size distribution of the particles on a volume basis by, for example, a laser diffraction type particle size distribution measuring device (LA-500 manufactured by HORIBA), and the median size (D50) thereof. ) Can be the average particle size.

The inorganic filler is not particularly limited, but an inorganic filler having a monodisperse average particle size may be used, or an inorganic filler having a polydisperse average particle size may be used. Further, one kind or two or more kinds of inorganic fillers having an average particle size of monodisperse and / or polydisperse may be used in combination.

The inorganic filler preferably contains silica particles. The silica particles may be spherical. The average particle size of the silica particles is not particularly limited, but may be, for example, 5.0 μm or less, 0.1 μm or more and 4.0 μm or less, or 0.2 μm or more and 2.0 μm or less. Thereby, the filling property of the inorganic filler can be further improved.

The lower limit of the content of the inorganic filler is not particularly limited with respect to 100% by mass of the total solid content of the resin composition, but for example, it is preferably 40% by mass or more, more preferably 50% by mass or more, and 60% by mass. The above is more preferable. As a result, the cured product of the resin film can have particularly low thermal expansion and low water absorption. Moreover, the warp of the semiconductor package can be suppressed. On the other hand, the upper limit of the content of the inorganic filler is not particularly limited with respect to 100% by mass of the total solid content of the resin composition, but may be, for example, 85% by mass or less, or 80% by mass or less. , 75% by mass or less. As a result, the handleability is improved and it becomes easy to form the resin film.

(Cyanate resin)
The resin composition may 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, but can be obtained, for example, by reacting a cyanide compound with a phenol or a naphthol and, if necessary, prepolymerizing by a method such as heating. In addition, a commercially available product prepared in this manner can also be used.
By using the cyanate resin, the coefficient of linear expansion of the cured product of the resin film can be reduced. Further, the electrical characteristics (low dielectric constant, low dielectric loss tangent), mechanical strength, etc. of the cured product of the resin film can be improved.

The cyanate resin is, for example, a novolak type cyanate resin; a bisphenol type cyanate resin such as a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, a tetramethylbisphenol F type cyanate resin; a naphthol aralkyl type phenol resin, and cyanate halide. Examples thereof include naphthol aralkyl type cyanate resin obtained by the reaction; dicyclopentadiene type cyanate resin; biphenylalkyl type cyanate resin and the like. Among these, novolak type cyanate resin and naphthol aralkyl type cyanate resin are preferable, and novolak type cyanate resin is more preferable. By using the novolak 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 novolak type cyanate resin forms a triazine ring after the curing reaction. Further, it is considered that the novolak type cyanate resin has a high proportion of benzene rings due to its structure and is easily carbonized. Further, the cured product of the resin film containing the novolak type cyanate resin has excellent rigidity. Therefore, the heat resistance of the cured product of the resin film can be further improved.

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

The average repeating unit n of the novolak type 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 more than the above lower limit value, the heat resistance of the novolak type cyanate resin is improved, and it is possible to suppress the desorption and volatilization of the low weight substance during heating. The average repeating unit n is not particularly limited, but is preferably 10 or less, and more preferably 7 or less. When n is not more than the above upper limit value, it is possible to suppress an increase in melt viscosity and improve the moldability of the resin film.

Further, 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-xylene glycol, α, α'-dimethoxy-p-xylene, 1,4. It is 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 of 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 is unlikely to occur during synthesis, liquid separation property during washing with water is improved, and a decrease in yield tends to be prevented.

（式中、Ｒはそれぞれ独立に水素原子またはメチル基を示し、ｎは１以上１０以下の整数を示す。）

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

Further, one type of cyanate resin may be used alone, two or more types may be used in combination, or one type or two or more types may be used in combination with their prepolymers.

The lower limit of the content of the cyanate resin is, for example, preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, based on 100% by mass of the total solid content of the resin composition. As a result, it is possible to achieve low linear expansion and high elastic modulus of the cured product of the 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 mass of the total solid content of the resin composition, but for example, it is preferably 30% by mass or less, more preferably 25% by mass or less, and 20% by mass. More preferably, it is by mass or less. Thereby, 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.

(Thermoplastic resin)
The resin composition may contain a thermoplastic resin.
Examples of the thermoplastic resin include phenoxy resin, acrylic resin, methacrylic resin, polyvinyl acetal resin, thermoplastic polyimide resin, polyamide resin, polyamideimide resin, polyphenylene oxide resin, polyether sulfone resin, polyester resin, polyethylene resin, and polystyrene. Examples thereof include resins, polysulfone resins, polybutadiene resins, ABS resins, and kumaron resins. As the above-mentioned thermoplastic resin, one of them may be used alone, or two or more kinds having different weight average molecular weights may be used in combination, and one kind or two or more kinds and their prepolymers may be used in combination. It may be used together.

Among these, the thermoplastic resin may include one or more selected from the group consisting of polyimide resin, polyamide resin, phenoxy resin and kumaron resin. A phenoxy resin may be used from the viewpoint of increasing the elongation of the cured product.

The phenoxy resin is not particularly limited, but for example, a phenoxy resin having a bisphenol A skeleton, a phenoxy resin having a bisphenol F skeleton, a phenoxy resin having a bisphenol S skeleton, and bisphenol M (4,4'-(1,3-). Phenoxy resin with phenylenediisopridiene) bisphenol) skeleton, bisphenol P (4,4'-(1,4) -phenylenediisopridiene) bisphenol) Phenoxy resin with skeleton, bisphenol Z (4,4'- Cyclohexidiene bisphenol) Phenoxy resin with bisphenol skeleton Phenoxy resin with bisphenol skeleton, phenoxy resin with novolak skeleton, phenoxy resin with anthracene skeleton, phenoxy resin with fluorene skeleton, phenoxy resin with dicyclopentadiene skeleton, norbornene skeleton Examples thereof include a phenoxy resin having a naphthalene skeleton, a phenoxy resin having a biphenyl skeleton, and a phenoxy resin having an adamantan skeleton. Further, as the phenoxy resin, a structure having a plurality of types of skeletons among them can be used, or a phenoxy resin having a different ratio of each skeleton can be used. Further, a plurality of types of phenoxy resins having different skeletons can be used, a plurality of types of phenoxy resins having different weight average molecular weights can be used, and prepolymers thereof can be used in combination.

The lower limit of the weight average molecular weight (Mw) of the phenoxy resin is, for example, 10,000 or more, preferably 15,000 or more, and more preferably 20,000 or more. This makes it possible to improve the compatibility with other resins and the solubility in a solvent. On the other hand, the upper limit of the weight average molecular weight (Mw) of the phenoxy resin is, for example, 60,000 or less, preferably 55,000 or less, and more preferably 50,000 or less. As a result, the film forming property is improved, and it is possible to suppress the occurrence of defects when used in the manufacture of a printed wiring board.

As the kumaron resin, one containing a structural unit derived from a kumaron-based monomer can be used. The kumaron resin may have a structural unit derived from a monomer other than the kumaron-based monomer. Examples of other monomers include indene-based monomers and styrene-based monomers. The kumaron resin may be composed of a copolymer of these other monomers. The kumaron resin can have a repeating structure of these structural units.

The content of the thermoplastic resin (for example, phenoxy resin) is not particularly limited, but is preferably 0.5% by mass or more and 40% by mass or less, and 1% by mass or more and 20% by mass or less with respect to the entire resin composition. More preferred. When the content is at least the above lower limit value, it is possible to suppress a decrease in the mechanical strength of the insulating layer and a decrease in the plating adhesion between the insulating layer and the conductor circuit. When it is not more than the above upper limit value, 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 resin composition may contain a curing accelerator (curing catalyst). Thereby, the curability of the resin composition can be improved.

As the curing accelerator, one that accelerates the curing reaction of the thermosetting resin can be used, and the type thereof is not particularly limited. In the present embodiment, as the curing 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, etc. , Pyridine, 4-dimethylaminopyridine, p-dimethylaminopyridine, N-methylmorpholin, quinoline, isoquinoline, pyrimidine, piperazine and other nitrogen-containing heterocyclic compounds, phenol, bisphenol A, nonylphenol and other phenolic compounds, acetic acid, benzo It can contain one or more selected from acids, organic acids such as salicylic acid, paratoluenesulfonic acid, and onium salt compounds. Among these, from the viewpoint of more effectively improving the curability, it is more preferable to contain imidazoles, nitrogen-containing heterocyclic compounds or onium salt compounds.

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

（上記一般式（２）中、Ｐはリン原子、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ、置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を示し、互いに同一であっても異なっていてもよい。Ａ⁻は分子外に放出しうるプロトンを少なくとも１個以上分子内に有するｎ（ｎ≧１）価のプロトン供与体のアニオン、またはその錯アニオンを示す）

(In the above general formula (2), P is a phosphorus atom, and R ³ , R ⁴ , R ⁵ and R ⁶ are organic groups having substituted or unsubstituted aromatic rings or heterocycles, respectively, or substituted or unsubstituted. They represent aliphatic groups and may be the same or different from each other. A ⁻ is an anion of an n (n ≧ 1) -valent proton donor having at least one or more protons that can be released to the outside of the molecule. , Or its complex anion)

Further, a radical initiator may be used as the curing accelerator.
As the radical initiator, for example, an organic peroxide or an azo compound such as azobisisobutyronitonyl can be used. Of these, it is preferable to use an organic peroxide.
Here, examples of the organic peroxide include 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanate, t-butylperoxy-2-ethylhexanate, and t-hexylperoxy-2. -Ethylhexanate, t-butylperoxy-2-ethylhexyl monocarbonate, t-butylperoxybenzoate, t-butylcumyl peroxide, dicumyl peroxide, 1,1-bis (t-butylperoxy) -3 , 3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, α, α'-di (t-butylperoxy) diisopropylbenzene, 2,5- Examples thereof include dimethyl-2,5-di (t-butylperoxy) hexanebis (4-t-butylcyclohexyl) peroxydicarbonate.
These organic peroxides can be used alone or in combination of two or more.

The lower limit of the content of the curing accelerator may be, for example, 0.01% by mass or more, preferably 0.05% by mass or more, based on the entire resin composition. By setting the content of the curing accelerator to the above lower limit value or more, the curability of the resin composition can be improved more effectively. On the other hand, the upper limit of the content of the curing accelerator excluding the inorganic filler may be, for example, 4% by mass or less, preferably 2% by mass or less, based on the entire resin composition. By setting the content of the curing accelerator to the above upper limit value or less, the storage stability of the resin composition can be improved.

(Coupling agent)
The resin composition may contain a coupling agent. The coupling agent may be added directly at the time of preparing the resin composition, or may be added in advance to the inorganic filler. The wettability of the interface between the inorganic filler and each resin can be improved by using a coupling agent. Therefore, it is preferable to use a coupling agent, and the heat resistance of the cured product of the resin film can be improved. Further, by using a coupling agent, the adhesion with the copper foil can be improved. Further, since the moisture absorption resistance can be improved, the adhesion with the copper foil can be maintained even in a humidity environment.

Examples of the coupling agent include silane coupling agents such as epoxy silane coupling agents, cationic silane coupling agents, and aminosilane coupling agents, titanate-based coupling agents, and silicone oil-type coupling agents. One type of coupling agent may be used alone, or two or more types may be used in combination. In the present embodiment, the coupling agent may contain a silane coupling agent.
As a result, the wettability of the interface between the inorganic filler and each resin can be increased, and the heat resistance of the cured product of the resin film can be further improved.

Various types of silane coupling agents can be used, and examples thereof include epoxysilane, aminosilane, alkylsilane, ureidosilane, mercaptosilane, and vinylsilane.

Specific compounds include, for example, 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-benzenedimethanan, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glysidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, γ-ureidopropyltriethoxysilane, vinyltriethoxysilane, etc. Of these, epoxy silane, mercapto silane, and amino silane are preferable, and primary amino silane or anilino silane is more preferable as the amino silane.

The content of the coupling agent can be appropriately adjusted with respect to the specific surface area of the inorganic filler. The lower limit of the content of such a coupling agent may be, for example, 0.01% by mass or more, preferably 0.05% by mass or more, based on 100% by mass of the total solid content of the resin composition. Good. When the content of the coupling agent is at least the above lower limit value, the inorganic filler can be sufficiently coated, and the heat resistance of the cured product of the resin film can be improved. On the other hand, the upper limit of the content of the coupling agent may be, for example, 3% by mass or less, preferably 1.5% by mass or less, based on 100% by mass of the total solid content of the 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 to suppress the decrease in the bending strength and the like of the cured product of the resin film.

(Additive)
The resin composition of the present embodiment is a kind selected from the group consisting of dyes such as green, red, blue, yellow, and black, pigments such as black pigments, and pigments as long as the object of the present invention is not impaired. Additives other than the above components such as colorants, low stress agents, defoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, ion trapping agents, and rubber components including the above may be included. .. These may be used alone or in combination of two or more.

Examples of the above pigments include kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, strontium yellow, chromium hydroxide-containing, chromium oxide, cobalt aluminate, synthetic ultramarine blue and other inorganic pigments, polycyclic pigments such as phthalocyanine, and azo. Pigments and the like can be mentioned.
Examples of the dye include isoindolinone, isoindoline, quinophthalone, xanthene, diketopyrrolopyrrole, perylene, perinone, anthraquinone, indigoid, oxazine, quinacridone, benzimidazolone, violanthrone, phthalocyanine, azomethine and the like.

The resin composition may contain a rubber component.
The rubber component can include one or more selected from the group consisting of butadiene rubber, acrylic rubber, and silicone rubber.

The rubber component may be contained in the form of particles. Examples of such rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and silicone particles.

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

When the resin composition is varnish-like, the solid content of the resin composition may be, for example, 30% by mass or more and 80% by mass or less, and more preferably 40% by mass or more and 70% by mass or less. As a result, a resin composition having excellent workability and film forming property can be obtained.

In the varnish-like resin composition, each of the above-mentioned components is mixed with various components such as an ultrasonic dispersion method, a high-pressure collision type dispersion method, a high-speed rotation dispersion method, a bead mill method, a high-speed shear dispersion method, and a rotation / revolution type dispersion method. It can be prepared by dissolving, mixing and stirring in a solvent using a machine.

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

The resin film of the present embodiment can be obtained by forming a varnish-like resin composition into a film. For example, the resin film of the present embodiment can be obtained by removing the solvent from the coating film obtained by applying the varnish-like resin composition. In such a resin film, the solvent content can be 5% by mass or less with respect to the entire resin film. In the present embodiment, the step of removing the solvent may be carried out under the conditions of, for example, 100 ° C. to 150 ° C., 1 minute to 5 minutes. This makes it possible to sufficiently remove the solvent while suppressing the progress of curing of the resin film containing the thermosetting resin.

The resin film of the present embodiment may be composed of the resin film alone or may be configured to include a fiber base material inside.

(Prepreg)
The prepreg of the present embodiment is configured to include a fiber base material in the resin composition. The prepreg is obtained by impregnating the fiber base material with the above resin composition.
For example, the prepreg can be used as a sheet-like material obtained by impregnating a fiber base material with a resin composition and then semi-curing it. A sheet-like material having such a structure is excellent in various properties such as dielectric properties, mechanical and electrical connection reliability under high temperature and humidity, and is suitable for manufacturing an insulating layer of a printed wiring board.

In the present embodiment, the method of impregnating the fiber base material with the resin composition is not particularly limited, but for example, the resin composition is dissolved in a solvent to prepare a resin varnish, and the fiber base material is immersed in the resin varnish. Methods, a method of applying the resin varnish to the fiber base material by various coaters, a method of spraying the resin varnish on the fiber base material by spraying, a method of laminating both sides of the fiber base material with the resin film made of a resin composition, etc. Can be mentioned.

Examples of the fiber base material include a glass fiber base material such as glass fiber cloth and glass non-fiber cloth, an inorganic fiber base material such as fiber cloth or non-fiber cloth containing an inorganic compound other than glass, an aromatic polyamide-imide resin, and polyamide. Examples thereof include an organic fiber base material composed of organic fibers such as a resin, an aromatic polyester resin, a polyester resin, a polyimide resin, and a fluororesin. Among these base materials, when a glass fiber base material typified by glass woven fabric is used in terms of strength, the mechanical strength and heat resistance of the printed wiring board can be improved.

The thickness of the fiber base material is not particularly limited, but is preferably 5 μm or more and 150 μm or less, more preferably 10 μm or more and 100 μm or less, and further preferably 12 μm or more and 90 μm or less. By using a fiber base material having such a thickness, handleability during prepreg production can be further improved.
When the thickness of the fiber base material is not more than the above upper limit value, the impregnation property of the resin composition in the fiber base material is improved, and the occurrence of strand voids and deterioration of insulation reliability can be suppressed. Further, it is possible to facilitate the formation of through holes by a laser such as carbon dioxide, UV, or excimer. Further, when the thickness of the fiber base material is at least the above lower limit value, the strength of the fiber base material and the prepreg can be improved. As a result, the handleability can be improved, the prepreg can be easily produced, and the warp of the resin substrate can be suppressed.

As the glass fiber base material, for example, glass formed of one or more kinds of glass selected from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass and quartz glass. A fiber substrate is preferably used.

In this embodiment, the prepreg can be used, for example, to form an insulating layer in a build-up layer or an insulating layer in a core layer of a printed wiring board. When the prepreg is used to form an insulating layer in the core layer of a printed wiring board, for example, two or more prepregs are stacked and the obtained laminate is heat-cured to obtain an insulating layer for the core layer. You can also do it.

(Metal-clad laminate)
The laminated board of the present embodiment is a metal-clad laminated board in which a metal layer is arranged on at least one surface of the cured product of the prepreg.

Further, a method for manufacturing a metal-clad laminate using a prepreg is, for example, as follows.
Metal leaf is laminated on both the upper and lower sides or one side of the outer side of a laminate in which two or more prepregs or prepregs are laminated, and these are joined under high vacuum conditions using a laminator device or a Becquerel device, or the upper and lower sides of the outer side of the prepreg are used as they are. Overlay metal foil on both sides or one side. When two or more prepregs are laminated, the metal foil is laminated on the outermost upper and lower sides or one side of the laminated prepregs. Next, a metal-clad laminate can be obtained by heat-press molding a laminate in which a prepreg and a metal foil are laminated. Here, it is preferable to continue the pressurization until the end of cooling during the heat pressurization molding.

Examples of the metals constituting the metal foil include copper, copper-based alloys, aluminum, aluminum-based alloys, silver, silver-based alloys, gold, gold-based alloys, zinc, zinc-based alloys, nickel, nickel-based alloys, tin, and the like. Examples thereof include tin-based alloys, iron, iron-based alloys, Coval (trade name), 42 alloys, Inver, Super Inver and other Fe—Ni based alloys, W, Mo and the like. Among these, copper or a copper alloy is preferable as the metal constituting the metal foil 105 because it is excellent in conductivity, circuit formation by etching is easy, and it is inexpensive. That is, as the metal foil 105, a copper foil is preferable.
Further, as the metal foil, a metal foil with a carrier or the like can also be used.
The thickness of the metal foil is preferably 0.5 μm or more and 20 μm or less, and more preferably 1.5 μm or more and 18 μm or less.

(Resin film with carrier)
Next, the resin film with a carrier of this embodiment will be described.
FIG. 1 is a diagram showing an example of the configuration of the resin film 10 with a carrier.

An example of the resin film 10 with a carrier includes a carrier base material 30 and a resin film 20) made of a resin composition provided on the carrier base material 30.

The resin film 10 with a carrier may have a roll-like shape as shown in FIG. 1A or a rectangular single-wafer shape.

As the carrier base material 30, for example, a polymer film or a metal foil can be used. The polymer film is not particularly limited, but is, for example, heat resistant to polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, release papers such as polycarbonate and silicone sheets, fluororesins and polyimide resins. Examples thereof include a thermoplastic resin sheet having the above. The metal foil is not particularly limited, and is, for example, copper and / or copper-based alloy, aluminum and / or aluminum-based alloy, iron and / or iron-based alloy, silver and / or silver-based alloy, gold and gold-based alloy. , Zinc and zinc alloys, nickel and nickel alloys, tin and tin alloys and the like. Of these, a sheet made of polyethylene terephthalate is most preferable because it is inexpensive and the peel strength can be easily adjusted. As a result, it becomes easy to peel off from the resin film 10 with a carrier with an appropriate strength.

Further, the surface of the resin film 10 with a carrier may be exposed, for example, or may be covered with a protective film (cover film 50). As the protective film, a film having a known protective function can be used, but for example, a PET film may be used. As shown in FIG. 1B, the resin film 20 may be formed between the carrier base material 30 and the cover film 50. As a result, the handleability of the resin film 20 is improved.

The resin film 20 of the carrier-attached resin film 10 of the present embodiment may be a single layer or a multilayer, and may be composed of one type or two or more types of films. When the resin sheet has multiple layers, it may be composed of the same type or different types.

The lower limit of the film thickness of the resin film 20 is, for example, 5 μm or more, preferably 10 μm or more. Thereby, the insulation reliability can be improved. On the other hand, the upper limit of the film thickness of the resin film 20 is, for example, 50 μm or less, preferably 40 μm or less. As a result, it is possible to realize a thin layer of the printed wiring board. Further, by setting the thickness of the resin film 20 within the above range, it is possible to fill the unevenness of the inner layer circuit and mold it when manufacturing the printed wiring board, and the insulating resin layer of the suitable build-up layer. The thickness can be secured.

The thickness of the carrier base material 30 is not particularly limited, but may be, for example, 10 to 100 μm or 10 to 70 μm. This is preferable because the handleability when manufacturing the resin film 10 with a carrier is good.

(Printed wiring board)
The printed wiring board of the present embodiment includes an insulating layer made of a cured product of the resin film (cured product of the resin composition).
In the present embodiment, the cured product of the resin film is, for example, a build-up layer of a normal printed wiring board, a build-up layer of a printed wiring board having no core layer, a build-up layer of a coreless substrate used for PLP, and a MIS substrate. It can be used for the build-up layer of. The insulating layer constituting such a build-up layer is preferably used for the build-up layer constituting the printed wiring board in a large-area printed wiring board used for collectively producing a plurality of semiconductor packages. be able to.

Further, in the present embodiment, the resin film made of the resin composition for forming an insulating film can be configured to be impregnated with glass fibers. Even in a semiconductor package using such a resin film as a build-up layer, the coefficient of linear expansion of the cured product of the resin film can be lowered, so that the package warpage can be sufficiently suppressed.

(Semiconductor package)
FIG. 2 is a process cross-sectional view showing an example of the manufacturing process of the semiconductor package 200 of the present embodiment.
The semiconductor device (semiconductor package 200) of the present embodiment can include a printed wiring board and a semiconductor element 240 mounted on the circuit layer of the printed wiring board or built in the printed wiring board.

Hereinafter, an outline of the manufacturing process of the semiconductor package 200 of the present embodiment will be described.
First, as shown in FIG. 2A, a core layer 100 including an insulating layer 102, a via hole 104, and a metal layer 108 is prepared. A via hole 104 is formed in the insulating layer 102. A metal layer (via) is embedded in the via hole 104. The metal layer may be covered with the electroless metal plating film 106. The metal layer 108 (circuit layer having a predetermined circuit pattern) formed on the surface of the insulating layer 102 is electrically connected to the via formed in the via hole 104. In FIG. 2A, the metal layer 108 is formed on one surface of the core layer 100, but may be formed on both surfaces.

Subsequently, the resin film 20 made of the above resin composition is formed so as to embed the metal layer 108 on one surface of the core layer 100. For example, the cover film 50 may be peeled off from the carrier-attached resin film 10, and the resin film 20 (insulating film) may be arranged on the circuit forming surface of the core layer 100. A carrier base material 30 is provided on the surface of the resin film 20. The carrier base material 30 may be separated from the resin film 20 at this point, or may be used as a mask.
The resin film 20 may be a single layer of an insulating film, or may be composed of a plurality of layers of an insulating film and a primer layer.

Subsequently, an opening (not shown) is formed in the resin film 20 via the carrier base material 30. The opening can be formed to expose the metal layer 108. The method for forming the opening is not particularly limited, and for example, a laser processing method, an exposure development method, a blasting method, or the like can be used.

In the present embodiment, the resin film 20 may be thermoset after forming such an opening. After that, the carrier base material 30 is peeled off.

In addition, desmear processing can be performed as needed. In the desmear treatment, smear generated inside the opening can be removed and the surface of the resin film 20 can be roughened.

The method of the desmear treatment is not particularly limited, but can be performed as follows, for example. First, the core layer 100 on which the resin film 20 is laminated can be immersed in a swelling solution containing an organic solvent, and then immersed in an aqueous alkaline permanganate solution to neutralize and roughen the core layer 100. As the organic solvent, diethylene glycol monobutyl ether, ethylene glycol and the like can be used. Examples of such a swelling liquid include "Swelling Dip Securigant P" manufactured by Atotech Japan. As the permanganate salt, for example, potassium permanganate, sodium permanganate and the like can be used. The liquid temperature of the swelling liquid or the permanganate aqueous solution may be, for example, 50 ° C. or higher, or 100 ° C. or lower. The immersion time in the swelling solution or the permanganate aqueous solution may be, for example, 1 minute or more, or 30 minutes or less.

In the step of desmear treatment, only the above-mentioned wet desmear treatment can be performed, but plasma irradiation may be performed in addition to the desmear treatment.

Subsequently, the electroless metal plating film 202 is formed on the resin film 20 or the primer layer (not shown) formed on the resin film 20. An example of the electroless plating method will be described. For example, a catalyst nucleus is provided on the surface of the underlying layer. The catalyst nucleus is not particularly limited, but for example, a noble metal ion or a palladium colloid can be used. Subsequently, the electroless metal plating film 202 is formed by electroless plating with this catalyst nucleus as a core. For electroless plating, for example, those containing copper sulfate, formalin, complexing agent, sodium hydroxide and the like can be used. After electroless plating, heat treatment at 100 to 250 ° C. can be performed to stabilize the plating film.

Subsequently, as shown in FIG. 2B, a resist 204 having a predetermined opening pattern (opening 206) may be formed on the electroless metal plating film 202. This opening pattern corresponds to, for example, a circuit pattern. The resist 204 is not particularly limited, and known materials can be used, but liquid and dry films can be used. In the case of forming fine wiring, a photosensitive dry film or the like can be used as the resist 204. An example using a photosensitive dry film will be described. For example, a photosensitive dry film is laminated on the electroless metal plating film 202, a non-circuit forming region is exposed and photocured, and an unexposed portion is dissolved and removed with a developing solution. The resist 204 is formed by leaving the cured photosensitive dry film.

Subsequently, as shown in FIG. 2C, the electrolytic metal plating layer 208 is formed by electroplating at least inside the opening pattern of the resist 204 and on the electroless metal plating film 202. The electroplating is not particularly limited, but a known method used in a normal printed wiring board can be used. For example, a current is passed through the plating solution while being immersed in a plating solution such as copper sulfate. Etc. can be used. The electrolytic metal plating layer 208 may be a single layer or may have a multi-layer structure. The material of the electrolytic metal plating layer 208 is not particularly limited, and for example, any one or more of copper, copper alloy, 42 alloy, nickel, iron, chromium, tungsten, gold, and solder can be used.

Subsequently, as shown in FIG. 2D, the resist 204 is removed using an alkaline stripping solution, sulfuric acid, a commercially available resist stripping solution, or the like.

Subsequently, as shown in FIG. 2E, the electroless metal plating film 202 in the region (opening 210) other than the region where the electrolytic metal plating layer 208 is formed is removed. That is, the electroless metal plating film 202 of the lower layer is selectively removed by using the electrolytic metal plating layer 208 as a mask. For example, the electroless metal plating film 202 can be removed by using soft etching (flash etching) or the like. Here, the soft etching process can be performed, for example, by etching with an etching solution containing sulfuric acid and hydrogen peroxide. As a result, the metal layer 220 having a predetermined pattern can be formed. In this way, the metal layer 220 composed of the electroless metal plating film 202 and the electrolytic metal plating layer 208 is formed on the insulating layer made of the cured product of the resin film of the present embodiment by the semi-additive process (SAP). be able to.

Further, the build-up layer is laminated as necessary on the printed wiring board composed of the core layer 100 and the build-up layer, and the steps of interlayer connection and circuit formation by the semi-additive process are repeated to form multiple layers. can do.
From the above, the printed wiring board of this embodiment is obtained.

Subsequently, as shown in FIG. 2 (f), a build-up layer is laminated on the obtained printed wiring board as needed, and the steps of interlayer connection and circuit formation by a semi-additive process are repeated. Then, if necessary, the solder resist layer 230 is laminated on both sides or one side of the printed wiring board.

The method for forming the solder resist layer 230 is not particularly limited, but for example, a method of laminating a dry film type solder resist and forming it by exposure and development, or a method of printing a liquid resist and exposing and developing it. It is done by the method of forming.

Subsequently, by performing a reflow process, the semiconductor element 240 is fixed on the connection terminal which is a part of the wiring pattern via the solder bump 250. After that, the semiconductor element 240, the solder bump 250, and the like are sealed so as to be covered with the sealing material layer 260.
As a result, the semiconductor package 200 shown in FIG. 2 (f) is obtained.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the range in which the object of the present invention can be achieved are included in the present invention.

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 resin composition)
Each component is dissolved or dispersed in the solid content ratio shown in Table 1, adjusted to have a non-volatile content of 70% by mass with methyl ethyl ketone, and stirred using a high-speed stirrer to form a varnish-like resin composition (resin varnish P). Was prepared.
The numerical value indicating the blending ratio of each component in Table 1 indicates the blending ratio (mass%) of each component with respect to the total solid content of the resin composition.

The details of the raw materials of each component in Table 1 are as follows.
(Maleimide compound)
Maleimide compound 1: Imide-extended bismaleimide (BMI-1500, bismaleimide compound represented by the above formula (a1), manufactured by Digigner Moleculars, molecular weight 1500).
-Maleimide compound 2: In the above formula (1), n ₁ is 0 or more and 3 or less, X ₁ is a group represented by "-CH _2- ", a is 0, and b is 0 (BMI-2300, Made by Yamato Kasei Kogyo Co., Ltd., Mw = 750)
-Maleimide compound 3: Bisphenol A diphenyl ether Bismaleimide (BMI-4000, manufactured by Daiwa Kasei Kogyo Co., Ltd.)

(Allyl compound)
-Allyl compound 1: Allyl compound having an alicyclic structure in the molecule (manufactured by Gunei Chemical Industry Co., Ltd., FTC809AE, weight average molecular weight: 2,000)
-Allyl compound 2: Allyl compound having an alicyclic structure in the molecule (manufactured by Gunei Chemical Industry Co., Ltd., FATC809, weight average molecular weight: 2,700)
-Allyl compound 3: Liquid o-allylphenol formaldehyde novolak resin (manufactured by Meiwa Kasei Co., Ltd., MEH-8000H, phenolic compound having the structure of the following formula 2)

（式２中、ｍは０以上１０以下の整数を表し、Ｒ^１は水素原子、炭素数１以上１０以下のアルキル基、アリール基、アリル基、ビニル基から選ばれる１価の基を表す。）

(In Formula 2, m represents an integer of 0 or more and 10 or less, and R ¹ represents a monovalent group selected from a hydrogen atom, an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group, an allyl group, and a vinyl group. )

-Allyl compound 4: 2,2-bis (4-allyloxyphenyl) propane represented by the following chemical formula (manufactured by Sigma-Aldrich)

(Polymerization initiator)
-Polymerization initiator 1: Organic peroxide (manufactured by Tokyo Chemical Industry Co., Ltd., dicumyl peroxide)

(Inorganic filler)
-Inorganic filler 1: Silica particles (manufactured by Admatex, SC4050, average particle size 1.1 μm, surface treated with aminophenyl silicate)

Using the obtained resin varnish P (resin composition) in each Example and each Comparative Example, a resin film with a carrier, a printed wiring board, and a semiconductor package were prepared as follows.

(Resin film with carrier: Preparation of resin sheet)
The obtained resin varnish P was applied to one side of a PET film having a thickness of 38 μm using a comma coater device so that the total thickness of the resin layers after drying was 30 μm, and this was applied with a drying device at 160 ° C. After drying for 3 minutes, a resin sheet (resin film with a carrier) in which an insulating film was laminated on the PET film was obtained.

(Making a printed wiring board)
A laminate was produced from a resin sheet (resin film 1 with a carrier) having a thickness of 30 μm using a two-stage build-up laminator (CVP300 manufactured by Nichigo Morton). Specifically, using ELC-4785TH-G (manufactured by Sumitomo Bakelite Co., Ltd., copper foil 12 μm) having a thickness of 100 μm, a predetermined hole is opened with a drilling machine, and electroless plating is used to achieve conduction and copper foil. Was etched to prepare a core layer of 60% residual copper having a circuit forming surface. Further, the resin film of the resin film with a carrier was cut into a single sheet, set on the CVP 300, temporarily attached to the core layer, and vacuum-laminated in a vacuum laminator at 120 ° C. for 0.7 MPa for 30 seconds.
Then, using the hot press apparatus provided in the CPV300 manufactured by Nichigo Morton, the smoothing was performed by hot pressing at 100 ° C., 0.6 MPa for 60 seconds.
Then, the obtained laminate was placed in a hot air drying device at 160 ° C. for 60 minutes to carry out a curing reaction of the thermosetting resin of the build-up prepreg.
Next, via holes were formed in the obtained laminated plate by a carbon dioxide laser. After peeling off the PET film, the inside of the via and the surface of the resin layer are immersed in a swelling solution (Atotech Japan, Swelling Dip Securigant P) at 60 ° C for 5 minutes, and then an aqueous solution of potassium permanganate at 80 ° C (Aqueous solution of potassium permanganate at 80 ° C). Concentrate Compact CP manufactured by Atotech Japan Co., Ltd .: Sodium permanganate concentration 60 g / l, NaOH concentration 45 g / l) was immersed for 30 minutes, then neutralized and roughened.
After undergoing the steps of degreasing, applying a catalyst, and activating this, an electroless copper plating film of about 0.5 μm was formed to form a resist, and the pattern electroplated copper 20 μm was formed using the electroless copper plating film as a feeding layer. Circuit processing was applied. Next, an annealing treatment was performed at 200 ° C. for 60 minutes in a hot air drying device, and then the feeding layer was removed by flash etching. Next, a solder resist layer was formed, and an opening was formed so that a pad for mounting a semiconductor element or the like was exposed. Finally, a plating layer composed of an electroless nickel plating layer of 3 μm and an electroless gold plating layer of 0.1 μm is formed on the circuit layer exposed from the solder resist layer, and the obtained substrate is 50 mm. It was cut into a size of × 50 mm to obtain a printed wiring board.

(Manufacturing of semiconductor package)
In the semiconductor package, a semiconductor element (TEG chip, size 10 mm × 10 mm, thickness 0.1 mm) having solder bumps was mounted on the obtained printed wiring board by heat crimping with a flip chip bonder device. Next, after the solder bumps were melt-bonded in an IR reflow furnace, a liquid sealing resin (CRP-4152S manufactured by Sumitomo Bakelite Co., Ltd.) was filled, and then the liquid sealing resin was cured to obtain a semiconductor package. The liquid sealing resin was cured under the conditions of a temperature of 150 ° C. for 120 minutes. As the solder bump of the semiconductor element, one formed by eutectic having a Sn / Pb composition was used. Finally, it was separated into pieces with a router to a size of 14 mm × 14 mm to obtain a semiconductor package.

The resin film with a carrier, the printed wiring board, and the semiconductor package obtained by using the above resin varnish P (resin composition) were evaluated based on the following evaluation items.

(Dissipation factor)
Four resin films having a thickness of 30 μm with a carrier were laminated and heated and pressed for 2 hours at 200 ° C. and 1 kgf / mm ² using a hot press using a copper foil to cure the resin films. I let you. Next, the copper foil of the obtained cured product was removed by etching to produce a cured product as a sample.
The dielectric loss tangent at 1 GHz was measured for the obtained cured product by the cavity resonator method.

(Peel strength)
Using the obtained printed wiring board, the peel strength at 23 ° C. after the above-mentioned roughening treatment was measured according to JIS C-6481: 1996.

(Hygroscopic heat resistance test)
The obtained semiconductor package is pretreated in accordance with JEDEC (level 1) at a temperature of 85 ° C., a humidity of 85%, and a time of 168 hours, and then passed through a reflow furnace reaching 260 ° C. 10 times for ultrasonic flaw detection. The equipment evaluated the plating in the vias and the plating on which the wiring was formed. Each code in Table 1 is as follows.
◯: No plating swelling △: Up to 2 reflows, no plating swelling ×: No plating swelling with 1 or less reflows

(Smear removal property)
After the formation of via holes (VH) with a carbon dioxide laser and desmear, the bottom of the via was confirmed with a scanning electron microscope (SEM) for smear residue. As the evaluation sample, 50 VHs that had undergone the laser processing and the desmear treatment at the time of forming the outer layer circuit were arbitrarily selected.
Each code is as follows.
⊚: Good, no residue at all ○: No problem, there is a residue less than 5 μm from the VH wall surface Δ: Virtually unusable, there is a residue of 5 μm or more from the VH wall surface ×: Unusable, there is a residue on the entire via bottom

(Insulation)
The insulation reliability of the obtained printed wiring board with a fine circuit pattern of L / S = 15/15 μm was evaluated. The continuous wet insulation resistance was evaluated under the conditions of a temperature of 130 ° C., a humidity of 85%, and an applied voltage of 3.3 V. A resistance value of 106 Ω or less was regarded as a failure. The evaluation criteria are as follows.
◯: No failure for 500 hours or more Δ: Failure in 200 to less than 500 hours (substantially no problem)
×: There is a failure in less than 200 hours

The resin compositions of Examples 1 to 6 had a lower dielectric loss tangent and a higher peel strength (SAP characteristics) than those of Comparative Examples 1 and 2. Such resin compositions of Examples 1 to 6 can be suitably used for forming a circuit board.

10 Resin film with carrier 20 Resin film 30 Carrier base material 50 Cover film 100 Core layer 102 Insulation layer 104 Via hole 106 Electrolytic metal plating film 108 Metal layer 200 Semiconductor package 202 Electrolytic metal plating film 204 Resist 206 Opening 208 Electrolytic metal plating Layer 210 Opening 220 Metal layer 230 Solder resist layer 240 Semiconductor element 250 Solder bump 260 Encapsulant layer

Claims (11)

A resin composition for circuit boards
An allyl compound having an alicyclic structure in the molecule,
Maleimide compound and
Polymerization initiator and
A resin composition comprising, and an inorganic filler. The resin composition according to claim 1.
A resin composition having a weight average molecular weight of the allyl compound of 1,000 to 5,000. The resin composition according to claim 1 or 2.
A resin composition containing a thermoplastic resin. The resin composition according to claim 3.
A resin composition containing one or more of the thermoplastic resins selected from the group consisting of polyimide resins, polyamide resins, phenoxy resins and kumaron resins. The resin composition according to any one of claims 1 to 4.
A resin composition in which the inorganic filler contains silica. The resin composition according to any one of claims 1 to 5.
A resin composition in which the polymerization initiator contains a peroxide. Carrier base material and
A resin film made of the resin composition according to any one of claims 1 to 6 provided on the carrier base material.
A resin film with a carrier. A prepreg containing a fiber base material in the resin composition according to any one of claims 1 to 6. A laminated plate having a metal layer arranged on at least one surface of the prepreg according to claim 8. A printed wiring board comprising an insulating layer made of a cured product of the resin composition according to any one of claims 1 to 6. The printed wiring board according to claim 10 and
A semiconductor device including a semiconductor element mounted on a circuit layer of the printed wiring board or built in the printed wiring board.

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