JP2014205755A - Resin composition for primer layer formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printed wiring board having a fine circuit dimension and exhibiting excellent insulation reliability, and a semiconductor package with suppressed warpage.SOLUTION: A resin composition for primer layer formation is used for forming a primer layer 105 interposed between an insulator layer 101 and a metal layer 103 and causing adhesion of the insulator layer 101 to the metal layer 103. The resin composition includes a naphthylene ether type epoxy resin represented by the general formula (1) shown below, a thermoplastic resin, and an inorganic filler.

Description

  The present invention relates to a resin composition for forming a primer layer.

  In recent years, with the demand for higher functionality of electronic devices, the integration of electronic components and the implementation of high-density packaging have progressed, and the miniaturization of semiconductor packages used in these electronic devices has rapidly progressed. ing. A printed wiring board used for a semiconductor package is required to have a high-density and fine circuit.

As a method for forming a fine circuit, an SAP (semi-additive process) method has been proposed.
In the SAP method, first, a roughening treatment is performed on the surface of the insulating layer, and an electroless metal plating film serving as a base is formed on the surface of the insulating layer. Next, the non-circuit forming portion is protected by the plating resist, and the copper thickness of the circuit forming portion is thickened by electrolytic plating. Thereafter, the plating resist is removed, and the electroless metal plating film other than the circuit forming portion is removed by flash etching, thereby forming a circuit on the insulating layer. In the SAP method, since the metal layer laminated on the insulating layer can be thinned, finer circuit wiring is possible.

  However, the conventional insulating layer has a problem that the electroless plating property is poor and the SAP method cannot be performed well. Then, the method of using the metal-clad laminated board which laminated | stacked the metal foil with a primer layer on the insulating layer is proposed (for example, patent document 1, 2). In this method, by forming a circuit on the surface of the primer layer obtained by removing the metal foil on the metal-clad laminate, the electroless plating property on the surface of the insulating layer is improved.

JP 2006-196863 A JP 2007-326962 A

  As miniaturization of the semiconductor package progresses, the thickness of the semiconductor element and the sealing material that have conventionally been responsible for most of the rigidity of the semiconductor package becomes extremely thin, and the semiconductor package is likely to warp. In addition, since the proportion of the printed wiring board as a component increases, the physical properties and behavior of the printed wiring board have a great influence on the warpage of the semiconductor package.

On the other hand, as lead-free solder progresses from the viewpoint of protecting the global environment, the maximum temperature in the reflow process that occurs when mounting semiconductor elements on a printed wiring board or mounting a semiconductor package on a mounting board becomes extremely high. It has become to. Since the melting point of commonly used lead-free solder is about 210 degrees, the maximum temperature during the reflow process is a level exceeding 260 degrees.
In general, the difference in thermal expansion between a semiconductor element and a printed wiring board on which the semiconductor element is mounted is very large. Therefore, the semiconductor package may be greatly warped in the reflow process performed when the semiconductor element is mounted on the printed wiring board.
Similarly, in the reflow process performed when the semiconductor package is mounted on the mounting substrate, the semiconductor package may be greatly warped.

  Therefore, the present invention provides a resin composition for forming a primer layer that can provide a printed wiring board having fine circuit dimensions and excellent insulation reliability, and capable of providing a semiconductor package in which warpage is suppressed. .

  The present inventors diligently studied about suppression of warpage of the semiconductor package. As a result, when the primer layer contains a naphthylene ether type epoxy resin, a thermoplastic resin, and an inorganic filler, it is possible to reduce the warpage of the semiconductor package while maintaining a good balance of characteristics such as fine wiring processability and insulation reliability. And reached the present invention.

According to the present invention,
A resin composition for forming a primer layer, which is used to form a primer layer that is interposed between an insulating layer and a metal layer and adheres the insulating layer and the metal layer,
A naphthylene ether type epoxy resin represented by the following general formula (1);
A thermoplastic resin;
An inorganic filler;
A resin composition for forming a primer layer is provided.

（上記一般式（１）式において、ｎは１以上２０以下の整数であり、lは１または２の整数であり、Ｒ_１はそれぞれ独立に水素原子、ベンジル基、アルキル基または下記一般式（２）で表される構造であり、Ｒ_２はそれぞれ独立に水素原子またはメチル基である。）

(In the general formula (1), n is an integer of 1 or more and 20 or less, l is an integer of 1 or 2, and R ₁ is independently a hydrogen atom, a benzyl group, an alkyl group, or the following general formula ( 2), and each R ₂ is independently a hydrogen atom or a methyl group.)

（上記一般式（２）式において、Ａｒはそれぞれ独立にフェニレン基またはナフチレン基であり、Ｒ_２はそれぞれ独立に水素原子またはメチル基であり、ｍは１又は２の整数である。）

(In the above general formula (2), Ar is each independently a phenylene group or a naphthylene group, R ₂ is each independently a hydrogen atom or a methyl group, and m is an integer of 1 or 2.)

Furthermore, according to the present invention,
A prepreg formed by impregnating at least one layer of a fiber base material with a resin composition containing a thermosetting resin and an inorganic filler;
A primer layer that is interposed between the metal layer formed on at least one surface of the prepreg and the prepreg, and causes the metal layer and the prepreg to adhere to each other;
A prepreg with a primer layer,
There is provided a prepreg with a primer layer, wherein the primer layer is formed using the primer layer-forming resin composition of the present invention.

Furthermore, according to the present invention,
Metal foil,
A primer layer formed on at least one surface of the metal foil;
A metal foil with a primer layer,
Provided is a metal foil with a primer layer, wherein the primer layer is formed using the primer layer-forming resin composition of the present invention.

Furthermore, according to the present invention,
An insulating layer comprising a thermosetting resin, an inorganic filler and a fiber substrate;
Metal foil laminated on both sides or one side of the insulating layer;
A primer layer having a thickness smaller than the thickness of the insulating layer and interposing between the insulating layer and the metal foil so as to adhere the insulating layer and the metal foil;
A metal-clad laminate having
Provided is a metal-clad laminate in which the primer layer is formed using the primer layer-forming resin composition of the present invention.

Furthermore, according to the present invention,
A printed wiring board obtained by subjecting the metal-clad laminate of the present invention to circuit processing is provided.

Furthermore, according to the present invention,
A semiconductor package is provided in which a semiconductor element is mounted on the printed wiring board of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, while being able to provide the printed wiring board which has a fine circuit dimension and is excellent in insulation reliability, the resin composition for primer layer formation which can provide the semiconductor package by which curvature was suppressed can be provided. .

It is sectional drawing which shows an example of a structure of the printed wiring board of embodiment which concerns on this invention. It is sectional drawing which shows an example of a structure of the printed wiring board of embodiment which concerns on this invention. It is sectional drawing which shows an example of a structure of the metal-clad laminated board of embodiment which concerns on this invention. It is sectional drawing which shows an example of a structure of the metal foil with a primer layer of embodiment which concerns on this invention. It is sectional drawing which shows an example of a structure of the prepreg with a primer layer of embodiment which concerns on this invention. It is sectional drawing which showed typically an example of the manufacturing method of the printed wiring board of embodiment which concerns on this invention. It is sectional drawing which shows an example of a structure of the semiconductor package of embodiment which concerns on this invention. It is sectional drawing which shows an example of a structure of the semiconductor package of embodiment which concerns on this invention. It is sectional drawing which shows an example of a structure of the semiconductor device of embodiment which concerns on this invention. It is sectional drawing which shows an example of a structure of the semiconductor device of embodiment which concerns on this invention.

  Embodiments of the present invention will be described below with reference to the drawings. In all the drawings, similar constituent elements are denoted by common reference numerals, and description thereof is omitted as appropriate. Moreover, the figure is a schematic diagram and does not necessarily match the actual dimensional ratio.

[Resin composition for forming primer layer]
First, the primer layer forming resin composition P according to this embodiment will be described. 1 and 2 are cross-sectional views showing an example of the configuration of a printed wiring board 100 according to an embodiment of the present invention.

  The primer layer-forming resin composition P is used to form a primer layer 105 that is interposed between the insulating layer 101 and the metal layer 103 so that the insulating layer 101 and the metal layer 103 are in close contact with each other. The insulating layer 101 and the metal layer 103 constitute a part of the printed wiring board 100 as shown in FIGS. 1 and 2, for example.

The metal layer 103 is, for example, a circuit layer. When the printed wiring board 100 is a multilayer printed wiring board, the metal layer 103 is a circuit layer in the core layer 111 or the buildup layer 117.
The insulating layer 101 is an insulating resin layer, for example. When the printed wiring board 100 is a multilayer printed wiring board, it is the insulating layer 101 in the core layer 111 or the buildup layer 117. Note that the primer layer 105 is also an insulating layer because it is insulating, but the primer layer 105 is not included in the insulating layer 101 in this embodiment.

  The primer layer forming resin composition P includes a naphthylene ether type epoxy resin, a thermoplastic resin, and an inorganic filler. Accordingly, it is possible to provide a printed wiring board having fine circuit dimensions and excellent insulation reliability, and a semiconductor package in which warpage is suppressed.

  Hereinafter, each component which comprises the resin composition P for primer layer formation is demonstrated.

(Naphthylene ether type epoxy resin)
The primer layer forming resin composition P according to this embodiment contains a naphthylene ether type epoxy resin as an essential component. Thereby, the curvature of the obtained semiconductor package can be reduced.

  The naphthylene ether type epoxy resin according to this embodiment is represented by the following general formula (1).

（上記一般式（１）式において、ｎは１以上２０以下の整数であり、lは１または２であり、Ｒ_１はそれぞれ独立に水素原子、ベンジル基、アルキル基または下記一般式（２）で表される構造であり、Ｒ_２はそれぞれ独立に水素原子またはメチル基である。）

(In the general formula (1), n is an integer of 1 or more and 20 or less, l is 1 or 2, and R ₁ is independently a hydrogen atom, a benzyl group, an alkyl group, or the following general formula (2) And each R ₂ is independently a hydrogen atom or a methyl group.)

（上記一般式（２）式において、Ａｒはそれぞれ独立にフェニレン基またはナフチレン基であり、Ｒ_２はそれぞれ独立に水素原子またはメチル基であり、ｍは１又は２の整数である。）

(In the above general formula (2), Ar is each independently a phenylene group or a naphthylene group, R ₂ is each independently a hydrogen atom or a methyl group, and m is an integer of 1 or 2.)

Since the naphthylene ether type epoxy resin represented by the general formula (1) has a naphthalene ring in the molecule, molecular motion is suppressed by the intermolecular interaction between the naphthalene rings. Therefore, the linear expansion coefficient of the obtained primer layer 105 can be reduced by including the naphthylene ether type epoxy resin represented by the general formula (1), and as a result, the warpage of the semiconductor package 300 is reduced. can do.
Moreover, since the naphthylene ether type epoxy resin represented by the general formula (1) has only one epoxy group bonded to each naphthalene ring, the distance between the epoxy groups is long, and a primer containing this The crosslink density of the primer layer 105 formed by the layer forming resin composition P does not become extremely high. Therefore, the curing shrinkage of the obtained primer layer 105 does not increase, and as a result, distortion of the primer layer 105 can be suppressed.
In addition, the naphthylene ether type epoxy resin represented by the general formula (1) has appropriate flexibility because the naphthalene rings are connected to each other by oxygen atoms, and distortion during molding of the resulting primer layer 105 is obtained. Can be suppressed.
For the above reasons, it is possible to reduce the warpage of the semiconductor package that occurs in a heating process such as a reflow process.

  The naphthylene ether type epoxy resin represented by the general formula (1) can be synthesized by, for example, a method described in JP-A-2007-231083.

  Examples of the naphthylene ether type epoxy resin represented by the general formula (1) include those represented by the following general formula (3).

（上記一般式（３）式において、ｎは１以上２０以下の整数であり、好ましくは１以上１０以下の整数であり、より好ましくは１以上３以下の整数である。Ｒはそれぞれ独立に水素原子または下記一般式（４）で表される構造であり、好ましくは水素原子である。）

(In the above general formula (3), n is an integer of 1 or more and 20 or less, preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 3 or less. R is independently hydrogen. (Atom or a structure represented by the following general formula (4), preferably a hydrogen atom)

（上記一般式（４）式において、ｍは１又は２の整数である。）

(In the above general formula (4), m is an integer of 1 or 2.)

  Examples of the naphthylene ether type epoxy resin represented by the general formula (3) include those represented by the following general formulas (5) to (9).

The content of the naphthylene ether type epoxy resin is not particularly limited, but when the total solid content of the primer layer forming resin composition P (that is, the component excluding the solvent) is 100% by mass, the content is 10% by mass or more. Preferably, 20 mass% or more is more preferable. When the content of the naphthylene ether type epoxy resin is not less than the above lower limit value, the handling property is improved and the primer layer 105 can be easily formed.
The content of the naphthylene ether type epoxy resin is not particularly limited, but is preferably 55% by mass or less and more preferably 40% by mass or less when the total solid content of the primer layer forming resin composition P is 100% by mass. preferable. When the content of the naphthylene ether type epoxy resin is not more than the upper limit, the mechanical strength, flame retardancy and low thermal expansion of the primer layer 105 can be improved.

(Thermoplastic resin)
The resin composition P for forming a primer layer according to this embodiment includes a thermoplastic resin as an essential component.
Thereby, the adhesiveness between the insulating layer 101 and the metal layer 103 can be improved, and the stress relaxation ability of the primer layer 105 can be improved. As a result, the insulation reliability of the obtained printed wiring board 100 can be improved. In addition, since the adhesion between the insulating layer 101 and the metal layer 103 is excellent, fine wiring processing of a circuit is possible.

According to the study of the present inventor, when the primer layer contains the naphthylene ether type epoxy resin and the inorganic filler, it is possible to reduce the warpage of the obtained semiconductor package while reducing the fine wiring processability. It has been clarified that the insulation reliability of the obtained printed wiring board is lowered.
As a result of intensive studies in view of the above circumstances, the present inventor has found that when the primer layer contains the naphthylene ether type epoxy resin and the inorganic filler, the adhesion between the metal layer and the primer layer decreases, and as a result It turned out that wiring workability falls and the insulation reliability of the printed wiring board obtained falls.
Therefore, the present inventor has further studied diligently. As a result, by including the thermoplastic resin in addition to the naphthylene ether type epoxy resin and the inorganic filler, the adhesion between the metal layer and the primer layer is improved. As a result, the warpage of the resulting semiconductor package is improved. It has been found that the fine wiring processability and the insulation reliability of the printed wiring board are improved, and the present invention has been completed.

Examples of the thermoplastic resin according to this embodiment include phenoxy resin, thermoplastic polyimide resin, polyamide resin, polyamideimide resin, polyphenylene oxide resin, polyethersulfone resin, polyester resin, polyethylene resin, polystyrene resin, and the like. Among these, from the viewpoint of further improving the adhesion between the insulating layer 101 and the metal layer 103, a polyamide resin, a thermoplastic polyimide resin, a polyamideimide resin, and a polyethersulfone resin are preferable, and a polyamide resin, a thermoplastic polyimide resin, and Polyamideimide resin is particularly preferred.
As the thermoplastic resin, one of these may be used alone, or two or more having different weight average molecular weights may be used in combination, or one or two or more and those prepolymers may be used in combination. May be.

Moreover, it is preferable that the thermoplastic resin which concerns on this embodiment contains a rubber component in the structure. By including the rubber component, the adhesion between the insulating layer 101 and the metal layer 103 can be further improved, and the stress relaxation ability of the primer layer 105 can be further improved. As a result, finer wiring processing becomes possible, and the insulation reliability of the obtained printed wiring board 100 can be further improved.
The rubber component to be reacted with the thermoplastic resin according to this embodiment may be either natural rubber or synthetic rubber, and may be a modified rubber or an unmodified rubber. The synthetic rubber is not particularly limited, and examples thereof include NBR (butadiene-acrylonitrile copolymer), acrylic rubber, polybutadiene, isoprene, carboxylic acid-modified NBR, hydrogen conversion polybutadiene, epoxy-modified polybutadiene, and the like. .
Carboxylic acid-modified, hydroxyl-modified, and epoxy-modified ones may be used to improve compatibility with thermoplastic resins, and hydrogen-converted synthetic rubber may be used to prevent thermal degradation, but NBR and polybutadiene should be used. Is more preferable.

  The polyamide resin is not particularly limited, and for example, a resin obtained by polycondensation of an acid and an amine can be used. Especially, the polyamide resin (aromatic polyamide resin) which has an aromatic ring from the point which heat resistance improves is preferable, and what is represented by following General formula (10) is more preferable. The “aromatic polyamide resin” as used herein includes those obtained by reacting an aromatic polyamide resin and a rubber component.

（上記一般式（１０）において、ｍは繰り返し単位数を表し、５０以上５，０００以下の整数である。Ａｒ_１、Ａｒ_２は２価の芳香族基を示し、同じでも異なっていてもよい。Ｘは、ゴム成分のセグメントを有する基を示す。）

(In the general formula (10), m represents the number of repeating units and is an integer of 50 to 5,000. Ar ₁ and Ar ₂ represent a divalent aromatic group, and may be the same or different. X represents a group having a segment of a rubber component.)

The rubber component to be reacted with the aromatic polyamide resin represented by the general formula (10) may be either natural rubber or synthetic rubber, and may be a modified rubber or an unmodified rubber. The synthetic rubber is not particularly limited, and examples thereof include NBR (butadiene-acrylonitrile copolymer), acrylic rubber, polybutadiene, isoprene, carboxylic acid-modified NBR, hydrogen conversion polybutadiene, epoxy-modified polybutadiene, and the like. .
In order to improve compatibility with polyamide, carboxylic acid-modified, hydroxyl-modified or epoxy-modified ones or hydrogen-converted synthetic rubbers may be used to prevent thermal degradation, but it is more preferable to use NBR and polybutadiene. preferable.
A more preferable aromatic polyamide resin is a polyamide resin having a phenolic hydroxyl group. By having a phenolic hydroxyl group, in addition to flexibility, it is excellent in compatibility with a thermosetting resin.
Examples of the polyamide resin having a phenolic hydroxyl group include those represented by the following formula (11).

（上記一般式（１１）において、ｍ、ｎは繰り返し単位数を表し、５０以上５，０００以下の整数である。Ａｒ_１、Ａｒ_２は２価の芳香族基を示し、同じでも異なっていてもよい。Ｘは、ゴム成分のセグメントを有する基を示す。）

(In the above general formula (11), m and n represent the number of repeating units and are integers of 50 or more and 5,000 or less. Ar ₁ and Ar ₂ represent a divalent aromatic group and are the same or different. X represents a group having a segment of a rubber component.)

  The aromatic polyamide resin and the rubber component are preferably used in such a composition that the aromatic polyamide resin is 30 wt% or more and 85 wt% or less, and the balance is the rubber component.

  It does not specifically limit as said polyimide resin, For example, what is obtained by making a diamine component and an acid dianhydride component react can be used.

  The polyamide-imide resin is not particularly limited as long as it is a polymer having an amide group and an imide group in the main chain, and can be synthesized from, for example, a dicarboxylic acid derivative and diisocyanate.

  The content of the thermoplastic resin is not particularly limited. However, when the total solid content of the primer layer forming resin composition P (that is, the component excluding the solvent) is 100% by mass, the content is 5% by mass to 40% by mass. It is preferable that it is 10 mass% or more and 30 mass% or less. When the content of the thermoplastic resin is within the above range, the adhesion of the palladium catalyst of the primer layer and the electroless plating property are excellent, and the low thermal expansion property is also excellent.

(Inorganic filler)
The primer layer forming resin composition P according to this embodiment includes an inorganic filler as an essential component. Thereby, the mechanical strength and rigidity of the primer layer 105 can be improved. Furthermore, the linear expansion coefficient of the primer layer 105 obtained can be reduced.

Examples of the inorganic filler include talc, alumina, glass, silica, mica, aluminum hydroxide, magnesium hydroxide and the like. As the inorganic filler, one of these may be used alone, or two or more may be used in combination.
Among these, silica is preferable, and fused silica (especially spherical fused silica) is particularly preferable in terms of excellent low thermal expansion. The shape of the silica includes a crushed shape and a spherical shape. To lower the melt viscosity of the resin composition P for forming the primer layer, a usage method suitable for the purpose such as using spherical silica is adopted.

The silica is preferably silica nanoparticles having an average particle diameter of 1 nm or more and 100 nm or less, more preferably 10 nm or more and 100 nm or less, and particularly preferably 10 nm or more and 70 nm or less. Further, although not particularly limited, it may be combined with silica particles having an average particle diameter of 0.1 μm or more and 5.0 μm or less. Thereby, silica can be uniformly contained in the primer layer forming resin composition P at a high concentration.
In addition, the average particle diameter of the silica can be measured by, for example, a dynamic light scattering method. Particles are dispersed in water with ultrasonic waves, and the particle size distribution of the particles is measured on a volume basis using a dynamic light scattering particle size distribution analyzer (manufactured by HORIBA, LB-550). The median diameter (D ₅₀ ) is the average particle diameter. And

The method for producing the silica is not particularly limited. For example, a combustion method such as a VMC (Vaporized Metal Combustion) method, a PVS (Physical Vapor Synthesis) method, a melting method in which crushed silica is melted by flame, a sedimentation method, a gel method, etc. Among these, the VMC method is particularly preferable.
The VMC method is a method in which silica particles are formed by putting silicon powder into a chemical flame formed in an oxygen-containing gas, burning it, and cooling it. In the VMC method, the particle diameter of the silica fine particles to be obtained can be adjusted by adjusting the particle diameter of the silicon powder to be charged, the amount to be charged, the flame temperature, etc., so that silica fine particles having different particle diameters can be produced.
Commercially available products such as NSS-5N (manufactured by Tokuyama) and Sicastar 43-00-501 (manufactured by Micromod) can also be used as the silica nanoparticles.

  The content of the inorganic filler is not particularly limited, but when the total solid content of the primer layer forming resin composition P (that is, the component excluding the solvent) is 100% by mass, it is 20% by mass to 80% by mass. Preferably, 30 mass% or more and 60 mass% or less are more preferable. When the content of the inorganic filler is within the above range, the primer layer 105 can have particularly low thermal expansion and low water absorption.

(Thermosetting resin)
The primer layer forming resin composition P may further include a thermosetting resin other than the naphthylene ether type epoxy resin. Thereby, the curvature of a semiconductor package can be reduced further.

Although it does not specifically limit as a thermosetting resin, It is preferable that it has a low linear expansion coefficient and a high elasticity modulus, and is excellent in the reliability of thermal shock property.
Specific examples of the thermosetting resin include epoxy resins other than naphthylene ether type epoxy resins, phenol resins, cyanate resins, bismaleimide resins, and benzoxazine resins. One of these may be used alone, or two or more having different weight average molecular weights may be used in combination, or one or two or more and those prepolymers may be used in combination.

  Examples of epoxy resins other than naphthylene ether type epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol E type epoxy resins, bisphenol S type epoxy resins, and bisphenol M type epoxy resins (4,4'- (1,3-phenylene diisopridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4 ′-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin Bisphenol type epoxy resins such as (4,4'-cyclohexyldiene bisphenol type epoxy resin); Novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin; Biphenyl type epoxy resin Arylalkylene type epoxy resins such as xylylene type epoxy resins and biphenyl aralkyl type epoxy resins; naphthol type epoxy resins, naphthalene diol type epoxy resins, bifunctional to tetrafunctional epoxy type naphthalene resins, binaphthyl type epoxy resins, naphthalene aralkyl type epoxy resins Naphthalene type epoxy resins such as: anthracene type epoxy resins; phenoxy type epoxy resins; dicyclopentadiene type epoxy resins; norbornene type epoxy resins; adamantane type epoxy resins; and fluorene type epoxy resins.

  As the epoxy resin, one of these may be used alone, two or more having different weight average molecular weights may be used in combination, and one or two or more thereof and a prepolymer thereof may be used in combination. May be.

  Among these epoxy resins, naphthol type epoxy resins such as naphthol type epoxy resins, naphthalene diol type epoxy resins, bifunctional to tetrafunctional naphthalene type epoxy resins, and naphthylene ether type epoxy resins are preferable. Since the naphthalene ring has a higher π-π stacking effect than the benzene ring, the low thermal expansion property and low thermal contraction property of the primer layer 105 can be improved. Furthermore, since the polycyclic structure has a high rigidity effect and the glass transition temperature is particularly high, the heat shrinkage change before and after reflow is small. As a naphthol type epoxy resin, for example, the following general formula (VII-1), as a naphthalene diol type epoxy resin, the following formula (VII-2), as a bifunctional or tetrafunctional epoxy type naphthalene resin, the following formula (VII-3): (VII-4) (VII-5).

（ｎは平均１以上６以下の数を示し、Ｒはグリシジル基または炭素数１以上１０以下の炭化水素基を示す。）

(N represents an average number of 1 to 6, and R represents a glycidyl group or a hydrocarbon group having 1 to 10 carbon atoms.)

  Although the weight average molecular weight (Mw) of an epoxy resin is not specifically limited, Mw300 or more is preferable and especially Mw800 or more is preferable. When Mw is equal to or greater than the lower limit, it is possible to suppress the occurrence of tackiness in the primer layer 105. Mw is not particularly limited, but Mw is preferably 20,000 or less, and particularly preferably Mw15,000 or less. When Mw is not more than the above upper limit value, a more uniform primer layer 105 can be obtained. The Mw of the epoxy resin can be measured by GPC, for example.

Although the said cyanate resin is not specifically limited, For example, it can obtain by making a halogenated cyanide compound, phenols, and naphthol react, and prepolymerizing by methods, such as a heating, as needed. Moreover, the commercial item prepared in this way can also be used.
The primer layer forming resin composition P can reduce the linear expansion coefficient of the primer layer 105 by using a cyanate resin as a thermosetting resin. Further, the cyanate resin is excellent in electrical characteristics (low dielectric constant, low dielectric loss tangent), mechanical strength, and the like.

  Examples of the cyanate resin include novolak-type cyanate resin, bisphenol A-type cyanate resin, bisphenol E-type cyanate resin, and tetramethylbisphenol F-type cyanate resin; reaction of naphthol aralkyl-type phenol resin with cyanogen halide Naphthol aralkyl type cyanate resin obtained by the following: dicyclopentadiene type cyanate resin; biphenyl alkyl 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 is increased and the heat resistance is improved.

The reason for this is that the novolak 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. Further, the primer layer 105 containing a novolac type cyanate resin has excellent rigidity. Therefore, the heat resistance of the primer layer 105 can be further improved.
As a novolak-type cyanate resin, what is shown by the following general formula (I) can be used, for example.

  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 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. When n is less than or equal to the above upper limit, an increase in melt viscosity can be suppressed, and the moldability of the primer layer 105 can be improved.

  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 -It is obtained by condensing a naphthol aralkyl type phenol resin obtained by reaction with di (2-hydroxy-2-propyl) benzene 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 primer layer 105 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.

（式中、Ｒは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 represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 10.)

Although the weight average molecular weight (Mw) of cyanate resin is not specifically limited, Mw500 or more is preferable and Mw600 or more is more preferable. When Mw is equal to or more than the above lower limit, the occurrence of tackiness can be suppressed when the primer layer 105 is produced, and when the primer layers 105 are in contact with each other, the primer layers 105 are attached to each other or the primer layer 105 is transferred. Can be suppressed. Mw is not particularly limited, but is preferably Mw 4,500 or less, and more preferably Mw 3,000 or less. Further, when Mw is not more than the above upper limit value, it is possible to suppress the reaction from being accelerated, and it is possible to suppress the occurrence of a defect in the primer layer 105 or the decrease in the peel strength between the primer layer 105 and the metal layer 103. be able to.
Mw of cyanate resin can be measured by GPC (gel permeation chromatography, standard substance: polystyrene conversion), for example.

  Moreover, cyanate resin may be used individually by 1 type, may use together 2 or more types which have different Mw, and may use 1 type, or 2 or more types, and those prepolymers together.

The bismaleimide resin is not particularly limited. For example, 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2 ′-[4- (4-maleimidophenoxy) phenyl ] Propane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide, N, N'-ethylenedimaleimide, N, N'-hexamethylenedi Examples include maleimide.
Examples of the polymaleimide include polyphenylmethane maleimide. One of these can be used alone, or two or more having different weight average molecular weights can be used in combination. Among these bismaleimide resins, 4,4′-diphenylmethane bismaleimide, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane, bis- (3- Ethyl-5-methyl-4-maleimidophenyl) methane is preferred.

  The content of the thermosetting resin other than the naphthylene ether type epoxy resin is not particularly limited, but when the total solid content of the primer layer forming resin composition P (that is, the component excluding the solvent) is 100% by mass. 1 mass% or more and 30 mass% or less are preferable, and 5 mass% or more and 20 mass% or less are more preferable. When the content of the thermosetting resin is not less than the above lower limit value, the handling property is improved and the primer layer 105 can be easily formed. When the content of the thermosetting resin is not more than the above upper limit value, the strength, flame retardancy, and low thermal expansibility of the primer layer 105 can be improved.

(Other additives)
In addition, additives such as a coupling agent and a curing agent can be appropriately blended in the primer layer forming resin composition P as necessary. The primer layer forming resin composition P used in the present embodiment can be suitably used in a liquid form in which the above components are dissolved and / or dispersed with an organic solvent or the like.

(Coupling agent)
By using the coupling agent, the wettability of the interface between the inorganic filler and each resin can be improved. Therefore, it is preferable to use a coupling agent, and the heat resistance of the primer layer 105 can be improved.

Examples of the coupling agent include an epoxy silane coupling agent, a cationic silane coupling agent, an amino silane coupling agent, a titanate coupling agent, and a silicone oil type coupling agent. A coupling agent may be used individually by 1 type, and may use 2 or more types together.
Thereby, the wettability with the interface of an inorganic filler can be made high, and thereby heat resistance can be improved more.

The addition amount of the coupling agent is not particularly limited because it depends on the specific surface area of the inorganic filler, but when the total solid content of the primer layer forming resin composition P (that is, the component excluding the solvent) is 100% by mass. 0.01 mass% or more and 1 mass% or less is preferable, and 0.05 mass% or more and 0.5 mass% or less are more 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 primer layer 105 can be improved. Further, 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 primer layer 105.

(Curing agent)
Examples of the curing agent include 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-2-phenylimidazole (1B2PZ) ) And the like; and catalyst-type curing agents such as Lewis acids such as BF ₃ complexes.
Also, for example, aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), metaxylylenediamine (MXDA), diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), diaminodiphenylsulfone (DDS) In addition to aromatic polyamines such as dicyandiamide (DICY), polyamine compounds containing organic acid dihydralazide, etc .; alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), and trimellitic anhydride Acid anhydrides including aromatic acid anhydrides such as acid (TMA), pyromellitic anhydride (PMDA) and benzophenone tetracarboxylic acid (BTDA); polyphenols such as novolac-type phenolic resins and phenolic polymers Nord compounds; polysulfide, thioester, polymercaptan compounds such as thioethers; isocyanate prepolymer, isocyanate compounds such as blocked isocyanate; polyaddition type curing agent such as an organic acids such as carboxylic acid-containing polyester resin can be used.
Furthermore, for example, phenolic resin-based curing agents such as novolak-type phenolic resins and resol-type phenolic resins; urea resins such as methylol group-containing urea resins; and condensation-type curing agents such as melamine resins such as methylol group-containing melamine resins It may be used. 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 its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol novolak Resin, novolak resin such as naphthol novolak resin; polyfunctional phenol resin such as triphenolmethane phenol resin; modified phenol resin such as terpene modified phenol resin and dicyclopentadiene modified phenol resin; phenylene skeleton and / or biphenylene skeleton Aralkyl type resins such as phenol aralkyl resins having phenylene and / or naphthol aralkyl resins having a biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F, etc. Type may be used in combination of two or more be used alone. Among these, the hydroxyl equivalent is preferably 90 g / eq or more and 250 g / eq or less from the viewpoint of curability.

  Although content of the said hardening | curing agent is not specifically limited, When the total solid content (namely, component except a solvent) of the resin composition P for primer layer formation is 100 mass%, 0.01 weight% or more and 5 weight% The following is preferable, and 0.1 to 2% by weight is more preferable. When the content of the curing agent is not less than the above lower limit, the effect of promoting curing can be sufficiently exerted. When the content of the curing agent is not more than the above upper limit value, the preservability of the primer layer 105 can be further improved.

  Further, the primer layer-forming resin composition P may include the above-described components such as pigments, dyes, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, and ion scavengers as necessary. Additives other than may be added.

  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 and other inorganic pigments, phthalocyanine polycyclic pigments, azo pigments, etc. Etc.

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

In the primer layer forming resin composition P described above, the ratio of each component is, for example, as follows.
When the total solid content (that is, the component excluding the solvent) of the primer layer forming resin composition P is 100% by mass, the proportion of the naphthylene ether type epoxy resin is preferably 10% by mass to 55% by mass. Yes, the ratio of the thermoplastic resin is 5% by mass or more and 40% by mass or less, the ratio of the inorganic filler is 20% by mass or more and 80% by mass or less, and the thermosetting other than the naphthylene ether type epoxy resin. The ratio of the resin is 1% by mass to 30% by mass, the ratio of the coupling agent is 0.01% by mass to 1% by mass, and the ratio of the curing agent is 0.01% by weight to 5% by weight. is there.
More preferably, the ratio of the naphthylene ether type epoxy resin is 20% by mass to 40% by mass, the ratio of the thermoplastic resin is 10% by mass to 30% by mass, and the ratio of the inorganic filler is 30 mass% or more and 60 mass% or less, the ratio of the thermosetting resin other than the naphthylene ether type epoxy resin is 5 mass% or more and 20 mass% or less, and the ratio of the coupling agent is 0.05 mass% or more. It is 0.5 mass% or less, and the ratio of a hardening | curing agent is 0.1 to 2 weight%.

The glass transition temperature (temperature increase rate 5 ° C./min, frequency 1 Hz) by dynamic viscoelasticity measurement of a cured product (primer layer) obtained by heating and curing the primer layer forming resin composition P at 200 ° C. for 1 hour is: Preferably they are 150 degreeC or more and 250 degrees C or less, More preferably, they are 150 degreeC or more and 220 degrees C or less.
The glass transition temperature can be measured using a dynamic viscoelasticity analyzer (DMA). When the glass transition temperature measured by dynamic viscoelasticity measurement of the cured product is within the above range, the rigidity and heat resistance of the primer layer 105 can be further improved.

The linear expansion coefficient (CTE) of a cured product (primer layer) obtained by heat-curing the resin composition P for forming a primer layer at 200 ° C. for 1 hour is preferably 75 ppm / ° C. or less, more preferably 60 ppm / ° C. It is as follows. Moreover, the minimum of the linear expansion coefficient of the said hardened | cured material is although it does not specifically limit, Usually, it is 5 ppm / degrees C or more.
In this embodiment, the linear expansion coefficient is a temperature range of 30 to 300 ° C., 10 ° C./min, and a load of 5 g using a TMA (thermomechanical analysis) device (TA Instruments, Q400). It is a linear expansion coefficient (CTE) of the plane direction (XY direction) in 50-150 degreeC of the 2nd cycle.
When the linear expansion coefficient of the cured product of the resin composition P for forming the primer layer is within the above range, it is possible to more effectively obtain the suppression of the warpage of the semiconductor package and the improvement of the temperature cycle reliability. Further, it is possible to more effectively improve the temperature cycle reliability with the motherboard of the semiconductor device in which the semiconductor package is secondarily mounted.
In addition, the linear expansion coefficient of this embodiment is an average value in the range of 50 degreeC or more and 150 degrees C or less.

Further, the primer layer formed by the primer layer forming resin composition P preferably has a sea-island structure, and at least the naphthylene ether type epoxy resin is present in the sea phase, and the thermoplastic resin is present in the island phase. Is preferred.
With such a structure, the stress relaxation ability of the primer layer 105 can be further improved. As a result, the insulation reliability of the obtained printed wiring board 100 can be further improved.

  Since the primer layer 105 formed from the primer layer forming resin composition P has good electroless plating property and can improve the adhesion between the insulating layer 101 and the metal layer 103, the circuit is formed by the SAP (semi-additive process) method. It can use suitably for the printed wiring board 100 to form.

  The thickness of the primer layer 105 is not particularly limited, but is usually 1 μm or more and 10 μm or less, preferably 2 μm or more and 8 μm or less. When the thickness of the primer layer 105 is within the above range, it is possible to obtain the printed wiring board 100 corresponding to the thinning without losing the characteristics of the insulating layer 101. The thickness of the primer layer 105 is preferably not less than the above lower limit for improving the insulation reliability, and is preferably not more than the above upper limit for achieving thinning, which is one of the purposes in the printed wiring board 100.

[Metal-clad laminate]
Next, the metal-clad laminate 280 according to this embodiment will be described. FIG. 3 is a cross-sectional view showing an example of the configuration of the metal-clad laminate 280 according to the embodiment of the present invention.

  The metal-clad laminate 280 includes an insulating layer 101 including a thermosetting resin (A), an inorganic filler (B), and a fiber substrate, a metal foil 255 laminated on both sides or one side of the insulating layer 101, and an insulating layer And a primer layer 105 that is interposed between the insulating layer 101 and the metal foil 255 and adheres the insulating layer 101 and the metal foil 255 to each other. The primer layer 105 is formed using the above-described primer layer forming resin composition P.

  Examples of the metal constituting the metal foil 255 include copper and copper alloys, aluminum and aluminum alloys, silver and silver alloys, gold and gold alloys, zinc and zinc alloys, nickel and nickel alloys, tin and Examples thereof include tin alloys, iron and iron alloys, Kovar (trade name), 42 alloys, Fe-Ni alloys such as Invar and Super Invar, W or Mo, and the like. Among these, as the metal constituting the metal foil 255, copper or a copper alloy is preferable because of its excellent conductivity, easy circuit formation by etching, and low cost. As the metal foil 255, a metal foil with a carrier can be used.

  The thickness of the metal foil 255 is preferably 0.5 μm or more and 20 μm or less, and more preferably 1.5 μm or more and 12 μm or less.

  The insulating layer 101 including the thermosetting resin (A), the inorganic filler (B), and the fiber base material contains, for example, a thermosetting resin (A) and an inorganic filler (B) as essential components. It is a prepreg formed by impregnating at least one layer of the fiber substrate with the product (I).

  Examples of the thermosetting resin (A) include cyanate resins, epoxy resins, maleimide resins, and phenol resins.

  The cyanate resin can be obtained, for example, by reacting a halogenated cyanide compound with a phenol and prepolymerizing it by a method such as heating as necessary. Specific examples include novolak-type cyanate resins, arylaralkyl-type cyanate resins, bisphenol A-type cyanate resins, bisphenol E-type cyanate resins, and bisphenol-type cyanate resins such as tetramethylbisphenol F-type cyanate resins. Among these, novolak-type cyanate resins and arylalkylene-type cyanate resins are preferable.

The weight average molecular weight of the cyanate resin is not particularly limited, but is preferably a weight-average molecular weight ^{5.0 × 10 2 ~4.5 × 10 3} , more preferably ^{6.0 × 10 2 ~3.0 × 10 3} . If it is smaller than this, tackiness may occur in the prepreg, and when the prepregs come into contact with each other, they may adhere to each other or transfer of the resin may occur. On the other hand, if it is larger than this, the reaction becomes too fast, which may cause molding failure or decrease the interlayer peel strength.

  Although content of cyanate resin is not specifically limited, 5 to 60 weight% of the whole resin composition (I) is preferable, and 10 to 50 weight% is further more preferable. By making content of cyanate resin etc. more than the said lower limit, a heat resistant fall can be prevented and thermal expansion can be reduced. Moreover, the fall of moisture resistance can be prevented by setting it as the said upper limit or less.

  Examples of the phenol resin include novolac type phenol resins, resol type phenol resins, aryl alkylene type phenol resins, and the like. Among these, arylalkylene type phenol resins are preferable. Thereby, moisture absorption solder heat resistance can be improved further. By using a phenol resin in combination with a cyanate resin, the reactivity of the cyanate resin can be improved, whereby the moldability of the insulating layer 101 is improved.

  Examples of the aryl alkylene type phenol resin include a xylylene type phenol resin and a biphenyl dimethylene type phenol resin.

  In particular, the combination of the novolac-type cyanate resin and the arylalkylene-type phenol resin can control the crosslinking density and improve the adhesion to the primer layer 105.

Although content of a phenol resin is not specifically limited, 1 to 55 weight% of the whole resin composition (I) is preferable, 5 to 40 weight% is more preferable, 8 to 20 weight% is more preferable. The following is more preferable. Heat resistance can be reliably improved by setting the phenol resin to the above lower limit or more, and low water absorption can be achieved by setting the phenol resin to the upper limit or less.
The weight average molecular weight of the phenol resin is not particularly limited, but is preferably 4 × 10 ^{2 to} 1.8 × 10 ^{3 and} more preferably 5 × 10 ^{2 to} 1.5 × 10 ³ . 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.

Although it does not specifically limit as an epoxy resin, For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol Z type epoxy resin (4,4'- cyclohexyleneene) Bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4 ′-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol M type epoxy resin (4,4 ′-(1,3- Bisphenol type epoxy resins such as phenylenediisopridiene) bisphenol type epoxy resins), novolak type epoxy resins such as phenol novolak type epoxy resins and cresol novolak type epoxy resins, biphenyl type epoxy resins, and xylylene type epoxy resins. Resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl dimethylene type epoxy resin, trisphenol methane novolak type epoxy resin, glycidyl ethers of 1,1,2,2- (tetraphenol) ethane, trifunctional, Or tetrafunctional glycidylamines, arylalkylene type epoxy resins such as tetramethylbiphenyl type epoxy resin, naphthalene skeleton modified cresol novolak type epoxy resin, methoxynaphthalene modified cresol novolak type epoxy resin, methoxynaphthalene dimethylene type epoxy resin, naphthol alkylene Naphthalene type epoxy resin such as epoxy resin, anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene Epoxy resins, adamantane type epoxy resins, fluorene type epoxy resins, flame-retarded epoxy resin or the like halogenated epoxy resins. One of these can be used alone, two or more having different weight average molecular weights can be used in combination, and one or two or more of these prepolymers can be used in combination.
Among these epoxy resins, one or more selected from the group consisting of biphenylaralkyl type epoxy resins, naphthalene skeleton-modified cresol novolak type epoxy resins, cresol novolak type epoxy resins, and naphthalene type epoxy resins are preferable. As a result, handling properties are improved, and heat resistance and flame retardancy are improved.

Although content of an epoxy resin is not specifically limited, 1 to 55 weight% of the whole resin composition (I) is preferable, and 2 to 40 weight% is more preferable. By making content of an epoxy resin more than the said lower limit, the fall of the moisture resistance of the product obtained can be prevented, preventing the fall of the reactivity of cyanate resin. Moreover, the heat resistance fall can be prevented by setting it as the said upper limit or less. The weight average molecular weight of the epoxy resin is not particularly limited, but is preferably 5 × 10 ² or more and 2 × 10 ³ or less, more preferably 8 × 10 ² or more and 1.5 × 10 ³ or less. When the weight average molecular weight is not less than the above lower limit value, tackiness is unlikely to occur in the prepreg, and by making it not more than the above upper limit value, it is possible to prevent a decrease in impregnation property to the fiber base material and to obtain a uniform product during prepreg production. There is an advantage that can be.

  The thermosetting resin (A) preferably includes at least a combination of a cyanate resin and an epoxy resin, or a combination of an epoxy resin and a phenol resin, and includes a combination of a cyanate resin, an epoxy resin, and a phenol resin. It is more preferable. In particular, when a metal-clad laminate is produced using a combination of a novolac type cyanate resin, a phenol resin, and a biphenyl aralkyl type epoxy resin, excellent dimensional stability can be obtained.

  Some of the cyanate resin, epoxy resin and phenol resin in the resin composition (I) are other thermosetting resins such as vinyl ester resin, melamine resin, maleimide resin, phenoxy resin, polyimide resin, polyamideimide resin, A thermoplastic resin such as polyphenylene oxide resin or polyethersulfone resin can also be used.

  Examples of the inorganic filler (B) include talc, alumina, glass, silica, mica and the like. Among these, silica is preferable, and fused silica is preferable in that it has excellent low expansibility. The shape is crushed and spherical, but in order to reduce the melt viscosity of the resin composition in order to ensure the impregnation property to the glass substrate, a usage method adapted to the purpose such as using spherical silica is adopted. .

  Although the average particle diameter of an inorganic filler (B) is not specifically limited, 0.01 micrometer or more and 5 micrometers or less are preferable, and 0.2 micrometer or more and 2 micrometers or less are more preferable. By setting it as the above lower limit, workability at the time of producing the prepreg is improved. Moreover, by setting it as the said upper limit, it can prevent that phenomena, such as sedimentation of an inorganic filler (B), generate | occur | produce in a varnish. Furthermore, spherical fused silica having an average particle diameter of 5 μm or less is preferable, and spherical fused silica having an average particle diameter of 0.01 μm to 2 μm is more preferable. Thereby, the filling property of an inorganic filler (B) can be improved. The average particle diameter can be measured using, for example, a laser light scattering particle size distribution measuring apparatus.

  The content of the inorganic filler (B) is preferably 30% by weight to 80% by weight and more preferably 40% by weight to 75% by weight of the entire resin composition (I). When the content of the inorganic filler (B) is within the above range, low thermal expansion and low water absorption can be achieved.

Although it does not specifically limit to resin composition (I), It is preferable to use a coupling agent further. By incorporating the coupling agent, the wettability of the interface between the thermosetting resin (A) and the inorganic filler (B) is improved, and the thermosetting resin (A) and the inorganic filler ( B) can be uniformly fixed to improve heat resistance, particularly solder heat resistance after moisture absorption. Any coupling agent can be used as long as it is normally used. Among them, an epoxy silane coupling agent, a titanate coupling agent, an aminosilane coupling agent, and a silicone oil coupling agent are selected. It is preferable to use one or more coupling agents. Since these coupling agents have high wettability with the inorganic filler (B) interface, the heat resistance can be further improved.
The blending amount of the coupling agent is desirably 0.05% by weight or more and 3% by weight or less with respect to the inorganic filler (B). By setting it to the above lower limit or higher, the inorganic filler (B) can be sufficiently coated to obtain sufficient heat resistance, and by setting the upper limit or lower, the influence on the reaction can be ignored. Further, it is possible to prevent a decrease in bending strength and the like.

  In the resin composition (I), a curing agent may be used as necessary. A well-known thing can be used as a hardening | curing agent. For example, zinc metal naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, zinc octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III) and the like, triethylamine, tributylamine, Tertiary amines such as diazabicyclo [2,2,2] octane, aromatic diamine compounds such as dicyandiamide, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2-phenyl-4-methylimidazole , Imidazoles such as 2-phenyl-4-methyl-5-hydroxyimidazole and 2-phenyl-4,5-dihydroxyimidazole, phenol compounds such as phenol, bisphenol A and nonylphenol, acetic acid, benzoic acid, salicylic acid, palato And organic acids such as toluenesulfonic acid, or a mixture thereof.

  If necessary, additives other than the above components can be added to the resin composition (I) as long as the characteristics are not impaired. Moreover, resin composition (I) can be obtained by adjusting a raw material and its compounding quantity suitably in the range which does not impair a characteristic.

Resin composition (I) is acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol, In organic solvents such as anisole, dissolution, mixing, etc. using various mixing machines such as ultrasonic dispersion method, high-pressure collision dispersion method, high-speed rotation dispersion method, bead mill method, high-speed shear dispersion method, and rotation and revolution dispersion method The resin varnish (I) can be obtained by stirring.
The solid content of the resin varnish (I) is not particularly limited, but is preferably 40% by mass or more and 80% by mass or less, and particularly preferably 50% by mass or more and 75% by mass or less. Thereby, the impregnation property to the fiber base material of resin varnish (I) can further be improved.

  Examples of the fiber base material include glass fiber base materials such as glass fiber cloth and glass non-fiber cloth, or inorganic fiber base materials such as fiber cloth and non-fiber cloth containing inorganic compounds other than glass, aromatic polyamideimide resin, polyamide resin, Examples thereof include organic fiber base materials composed of organic fibers such as aromatic polyester resins, polyester resins, polyimide resins, and fluororesins. Among these substrates, when a glass fiber substrate represented by a glass woven fabric is used in terms of strength and water absorption, the mechanical strength and heat resistance of the printed wiring board can be improved.

  Examples of the method of impregnating the fiber base material with the resin composition (I) include a method of immersing the fiber base material in a resin varnish, a method of applying with various coaters, and a method of spraying with a spray. Moreover, before impregnating a fiber base material with resin composition (I), after applying resin composition (I) to metal foil with a primer layer, resin composition (I) may be impregnated with a fiber base material. Good. Among these, the method of immersing the fiber base material in the resin varnish (I) is preferable. Thereby, the impregnation property of the resin composition with respect to the fiber base material can be improved. In addition, when a fiber base material is immersed in a resin varnish, a normal impregnation coating equipment can be used.

  It continues and demonstrates an example of the manufacturing method of the metal-clad laminated board 280. FIG.

  First, the metal foil 250 with a primer layer is produced. FIG. 4 is a cross-sectional view showing an example of the configuration of the metal foil 250 with a primer layer according to the embodiment of the present invention.

  The metal foil 250 with a primer layer includes a metal foil 255 and a primer layer 105 formed on at least one surface of the metal foil 255. The primer layer 105 is formed using the primer layer forming resin composition P described above. The metal foil 255 can be the same as described above.

First, the primer layer forming resin composition P according to the present embodiment is dispersed in an organic solvent using 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. A resin varnish (P) is produced by dissolving, mixing, and stirring using various types of mixers.
As the organic solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, or the like can be used.

  Next, the obtained resin varnish (P) is applied to the metal foil 255 to be in a semi-cured state, whereby the metal foil 250 with a primer layer can be obtained.

  Next, the resin varnish (I) is coated on the primer layer 105 of the metal foil 250 with a primer layer using various coating apparatuses, and then dried. Alternatively, the resin varnish (I) may be spray-coated on the primer layer 105 with a spray device and then dried. The drying conditions at this time may be any conditions as long as the primer layer 105 is semi-cured (becomes a B-stage state). Thereby, an insulating resin layer can be formed on the primer layer 105.

  Although the said coating apparatus is not specifically limited, For example, a roll coater, a bar coater, a knife coater, a gravure coater, a die coater, a comma coater, a curtain coater, etc. can be used. Among these, a method using a die coater, a knife coater, and a comma coater is preferable. Thereby, the insulating resin sheet with metal foil which has no void and has a uniform thickness of the insulating resin layer can be efficiently manufactured.

  In the insulating resin sheet with metal foil, the thickness of the insulating resin layer is usually 1 μm or more and 60 μm or less, preferably 5 μm or more and 50 μm or less.

  Next, the primer layer-attached prepreg 200 according to the present embodiment is produced. FIG. 5 is a cross-sectional view showing an example of the configuration of the primer layer-attached prepreg 200 according to the embodiment of the present invention.

  The prepreg 200 with a primer layer includes a prepreg 210 formed by impregnating at least one layer of a fiber base material 201 with a resin composition (I) containing a thermosetting resin (A) and an inorganic filler (B), and a prepreg And a primer layer 105 that is interposed between the metal foil 255 and the prepreg 210 that are formed on at least one surface of the 210, and causes the metal foil 255 and the prepreg 210 to adhere to each other. The prepreg 210 includes a fiber base 201 and a resin layer 203 (semi-cured state) made of the resin composition (I). The primer layer 105 is formed using the primer layer forming resin composition P described above. The metal foil 255 can be the same as described above. As the resin composition (I) containing the thermosetting resin (A) and the inorganic filler (B) and the fiber substrate 201, the same ones as described above can be used.

  First, two insulating resin sheets with metal foil in which the primer layer 105 and the insulating resin layer are sequentially laminated on the metal foil 255 are prepared. And it arrange | positions so that the insulating resin layer of an insulating resin sheet with a metal foil may oppose both surfaces of a sheet-like fiber base material. And, for example, heating is performed in a vacuum at 60 ° C. to 150 ° C., pressure is 0.1 MPa to 5 MPa and laminated from both sides of the insulating resin sheet with metal foil, and the fiber base material is impregnated with the resin constituting the insulating resin layer Let At this time, the primer layer 105 is still in a semi-cured state. Thereby, the prepreg 200 with a primer layer before heat-curing can be obtained.

  Next, the metal-clad laminate 280 can be obtained by directly heat-pressing the prepreg 200 with a primer layer. The temperature at the time of heat and pressure molding is not particularly limited, but is preferably 120 ° C. or higher and 250 ° C. or lower, particularly preferably 150 ° C. or higher and 230 ° C. or lower. The pressure at the time of heat and pressure molding is not particularly limited, but is preferably 0.1 MPa or more and 5 MPa or less, and particularly preferably 0.5 MPa or more and 3 MPa or less. By doing so, the primer layer 105 and the insulating resin layer are cured. In this embodiment, since the prepreg is prepared with a base material, the surface smoothness of the prepreg is high and low-pressure molding is possible. Further, if necessary, post-curing may be performed at a temperature of 150 ° C. or higher and 300 ° C. or lower in a high-temperature bath or the like.

The metal-clad laminate 280 can also be obtained by press-laminating the metal foil 250 with a primer layer on the insulating layer 101 with the primer layer 105 inside.
At this time, the metal foil 250 with a primer layer may be laminated | stacked only on the single side | surface of the insulating layer 101, and may be laminated | stacked on both surfaces.

  The metal-clad laminate 280 can also be manufactured by laminating the primer layer 105 on the surface of the insulating layer 101 and then laminating the metal foil 255 on the surface of the primer layer 105.

Furthermore, as another method for producing the metal-clad laminate 280, a method for producing a metal-clad laminate using a polymer film sheet with an insulating resin layer can also be mentioned. First, a primer layer 105 is formed on a polymer film sheet, and an insulating resin layer containing a thermosetting resin and an inorganic filler is formed thereon with a coater to produce an insulating resin sheet with a primer layer. Next, the obtained insulating resin sheet with a primer layer is arranged on both sides of the fiber base material with the insulating resin layer inside. Next, a prepreg with a polymer film sheet can be obtained, for example, by a method of laminating and impregnating at 60 to 130 ° C. and a pressure of 0.1 to 5 MPa in vacuum.
After removing the polymer film sheet of the obtained prepreg with a polymer film sheet, a prepreg 200 with a primer layer having a primer layer 105 on both sides was obtained, and then a metal foil was placed on the primer layer 105 of the prepreg and heated. The metal-clad laminate 280 can be obtained by pressure molding.

  The metal-clad laminate 280 may be a laminate of two or more prepregs.

  The printed wiring board 100 can be obtained using the metal-clad laminate 280 as a core substrate.

[Printed wiring board]
Next, the printed wiring board 100 according to the present embodiment will be described. 1 and 2 are cross-sectional views showing an example of the configuration of a printed wiring board 100 according to an embodiment of the present invention.

  The printed wiring board 100 includes at least an insulating layer 101 provided with a via hole 107, a primer layer 105 provided on at least one surface of the insulating layer 101, and a metal layer 103 formed on the primer layer 105. In the present embodiment, the via hole 107 is a hole for electrically connecting the layers, and may be either a through hole or a non-through hole.

  As shown in FIG. 1, the printed wiring board 100 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. The double-sided printed wiring board is a printed wiring board in which the metal layer 103 is laminated on both sides of the insulating layer 101. The multilayer printed wiring board is a print in which two or more metal layers 103 are laminated on the insulating layer 101 via an interlayer insulating layer (also referred to as a build-up layer) by a plated through hole method or a build-up method. It is a wiring board.

(Metal layer)
The metal layer 103 is, for example, a circuit layer, and includes an electroless metal plating film 108 and an electrolytic metal plating layer 109.

  The metal layer 103 is formed, for example, on the surface of the primer layer 105 that has been subjected to chemical treatment or plasma treatment by the SAP (semi-additive process) method. FIG. 6 is a cross-sectional view schematically showing an example of a method for manufacturing the printed wiring board 100 according to the embodiment of the present invention. After the electroless plating film 108 is applied on the primer layer 105 (FIG. 6 (d)), the non-circuit forming portion is protected by the plating resist 205 (FIG. 6 (e)), and the electrolytic metal plating layer 109 is applied by electrolytic plating. (FIG. 6F), the metal layer 103 is formed on the primer layer 105 by removing the plating resist 205 and removing the electroless metal plating film 108 by flash etching (FIG. 6G).

  The circuit dimension of the metal layer 103, when expressed in line and space (L / S), can be 25 μm / 25 μm or less, particularly 15 μm / 15 μm or less. If the circuit dimensions are reduced and the wiring is made fine, the adhesiveness decreases and the insulation reliability between the wirings decreases. However, the printed wiring board 100 according to the present embodiment is capable of fine wiring with a line and space (L / S) of 15 μm / 15 μm or less, and the line and space (L / S) can be refined to about 10 μm / 10 μm. Can be achieved.

  The thickness of the metal layer 103 is not particularly limited, but is usually 5 μm or more and 25 μm or less.

(Insulating layer)
The insulating layer 101 is provided with a via hole 107, for example.
The insulating layer 101 is an insulating resin layer, for example. When the printed wiring board 100 is a multilayer printed wiring board, it is the insulating layer 101 in the core layer 111 or the build-up layer 117 as shown in FIG. Note that the primer layer 105 is also an insulating layer because it is insulating, but the primer layer 105 is not included in the insulating layer 101 in this embodiment.

The insulating layer 101 in the core layer 111 (including the insulating layer 101 in the printed wiring board 100 that does not include the build-up layer 117) is not particularly limited as long as it is made of an insulating material. , Glass substrate-epoxy resin laminate, glass substrate-polyimide resin laminate, glass substrate-Teflon (registered trademark) resin laminate, glass substrate-bismaleimide / triazine resin laminate, glass substrate-cyanate resin It can be composed of a laminated plate, a glass substrate-polyphenylene ether resin laminated plate, a polyester resin, a ceramic, a resin-impregnated ceramic, a prepreg, or the like. Among these, the prepreg is a sheet-like material, and is excellent in various properties such as dielectric properties, mechanical and electrical connection reliability under high temperature and high humidity, and suitable for the production of the core layer 111 for a printed wiring board. .
As the prepreg, the above-described prepreg 210 or the prepreg 200 with a primer layer can be used.

The insulating layer 101 in the build-up layer 117 is not particularly limited as long as it is made of an insulating material, but can be made of, for example, a resin film or a prepreg. Among these, the prepreg is a sheet-like material, which has excellent dielectric properties, various properties such as mechanical and electrical connection reliability under high temperature and high humidity, and is suitable for manufacturing the build-up layer 117 for a printed wiring board. preferable.
As the prepreg, the above-described prepreg 210 or the prepreg 200 with a primer layer can be used.

  The thickness of the insulating layer 101 in the core layer 111 (including the insulating layer 101 in the printed wiring board 100 that does not include the build-up layer 117) is preferably 0.025 mm or more and 0.6 mm or less, and more preferably It is 0.04 mm or more and 0.4 mm or less, more preferably 0.04 mm or more and 0.3 mm or less, and particularly preferably 0.05 mm or more and 0.2 mm or less. When the thickness of the insulating layer 101 is within the above range, the balance between mechanical strength and productivity is particularly excellent, and the insulating layer 101 suitable for a thin printed wiring board can be obtained.

  The thickness of the insulating layer 101 in the buildup layer 117 is preferably 0.01 mm or greater and 0.1 mm or less, and more preferably 0.015 mm or greater and 0.05 mm or less. When the thickness of the insulating layer 101 is within the above range, the balance between mechanical strength and productivity is particularly excellent, and the insulating layer 101 suitable for a thin printed wiring board can be obtained.

  In the printed wiring board 100, the peel strength between the insulating layer 101 and the metal layer 103, which is measured according to JIS C-6481: 1996, is preferably 0.5 kN / m or more, and more preferably. Is 0.6 kN / m or more. When the peel strength is not less than the above lower limit value, the peeling of the metal layer 103 can be further suppressed, and as a result, the insulation reliability between the wirings of the printed wiring board 100 can be further improved.

(Primer layer)
As shown in FIG. 1, the primer layer 105 is interposed between the insulating layer 101 and the metal layer 103 and is formed of the above-described primer layer forming resin composition P.
When the primer layer 105 further includes a buildup layer 117 as shown in FIG. 2, the insulating layer 101 and the metal layer between the insulating layer 101 and the metal layer 103 in the core layer 111 and between the insulating layer 101 and the metal layer 103 in the buildup layer 117. 2 as long as it is interposed between at least one of the insulating layer 101 and the metal layer 103 and between the insulating layer 101 and the metal layer 103 in the core layer 111 and between the insulating layer 101 and the metal in the buildup layer 117 as shown in FIG. It is preferable to intervene between both layers 103.

[Printed wiring board manufacturing method]
Next, an example of a method for manufacturing the printed wiring board 100 will be described. However, the manufacturing method of the printed wiring board 100 according to the present embodiment is not limited to the following example. FIG. 6 is a cross-sectional view schematically showing an example of a method for manufacturing the printed wiring board 100 according to the embodiment of the present invention.

(Production of metal-clad laminate)
First, the metal-clad laminate 280 is produced by laminating the metal foil 255 on both surfaces or one surface of the insulating layer 101 via the primer layer 105 (FIG. 6A). The method described above can be used as a method for manufacturing the metal-clad laminate 280. The primer layer 105 may be laminated on only one surface of the insulating layer 101 or may be laminated on both surfaces.

  Next, the metal foil 255 is removed by an etching process (FIG. 6B).

Next, a via hole 107 is formed in the insulating layer 101 (FIG. 6C). The via hole 107 can be formed using, for example, a drilling machine or laser irradiation. Examples of the laser used for laser irradiation include an excimer laser, a UV laser, and a carbon dioxide gas laser.
Resin residues and the like after forming the via hole 107 may be removed by an oxidizing agent such as permanganate or dichromate.
Note that the via hole 107 may be formed in the insulating layer 101 before the metal foil 255 is removed by etching.

  Next, a chemical treatment or plasma treatment is performed on the surface of the primer layer 105 (FIG. 6C).

  The chemical treatment is not particularly limited, and examples thereof include a method using an oxidant solution having an organic substance decomposing action. Examples of the plasma treatment include a method of directly irradiating a target object with active species (plasma, radical, etc.) having a strong oxidizing action to remove organic residue.

Specific examples of the chemical treatment include a method of performing a swelling treatment on the surface of the primer layer 105, performing an etching by an alkali treatment, and subsequently performing a neutralization treatment.
Examples of the plasma treatment include a method of performing discharge by a high frequency power source of about several kHz to several tens of MHz in a gas atmosphere of several mTorr to several Torr. In addition, as a use gas, reactive gas, such as oxygen, or inert gas, such as nitrogen and argon, can be used, for example. Depending on the pressure and the type of gas used, the gas components activated by the plasma may cause chemical reactions, physical reactions due to collision (bombing) of the gas molecules themselves, or both. Surface fouling due to molecules can be removed. Cleaning by plasma treatment can be performed by, for example, a parallel plate method.
By the plasma treatment, it is possible to remove a strong resin composition residue that cannot be removed by cleaning with a chemical solution.

  Next, the metal layer 103 is formed. The metal layer 103 can be formed by a semi-additive process. This will be specifically described below.

  First, an electroless metal plating film 108 is formed on the surface of the primer layer 105 and the via hole 107 using an electroless plating method (FIG. 6D). Conduction of both sides of the printed wiring board 100 is intended. The via hole 107 can be appropriately filled with a conductor paste or a resin paste. An example of the electroless plating method will be described. For example, first, catalyst nuclei are provided on the surface of the primer layer 105. The catalyst nucleus is not particularly limited. For example, a noble metal ion or palladium colloid can be used. Subsequently, an electroless metal plating film 108 is formed by electroless plating using the catalyst nucleus as a nucleus. For electroless plating, for example, one containing copper sulfate, formalin, complexing agent, sodium hydroxide, or the like can be used. In addition, it is preferable to heat-process 100-250 degreeC after electroless plating, and to stabilize a plating film. A heat treatment at 120 to 180 ° C. is particularly preferable in that a film capable of suppressing oxidation can be formed. The average thickness of the electroless metal plating film 108 is, for example, about 0.1 to 2 μm.

  Next, a plating resist 205 having a predetermined opening pattern is formed on the electroless metal plating film 108 (FIG. 6E). This opening pattern corresponds to, for example, a circuit pattern. The plating resist 205 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, it is preferable to use a photosensitive dry film or the like as the plating resist 205. An example using a photosensitive dry film will be described. For example, a photosensitive dry film is laminated on the electroless metal plating film 108, the non-circuit formation region is exposed and photocured, and the unexposed portion is dissolved and removed with a developer. The plating resist 205 is formed by leaving the cured photosensitive dry film.

  Next, as shown in FIG. 6 (f), an electrolytic metal plating layer 109 is formed by electroplating at least inside the opening pattern of the plating resist 205 and on the electroless metal plating film 108. Although it does not specifically limit as electroplating, The well-known method used with a normal printed wiring board can be used, For example, an electric current is sent through a plating solution in the state immersed in plating solutions, such as copper sulfate. Etc. can be used. The electrolytic metal plating layer 109 may be a single layer or may have a multilayer structure. The material of the electrolytic metal plating layer 109 is not particularly limited, and for example, one or more of copper, copper alloy, 42 alloy, nickel, iron, chromium, tungsten, gold, and solder can be used.

  Next, as shown in FIG. 6G, the plating resist 205 is removed using an alkaline stripping solution, sulfuric acid, a commercially available resist stripping solution, or the like.

  Next, as shown in FIG. 6G, the electroless metal plating film 108 other than the region where the electrolytic metal plating layer 109 is formed is removed. For example, the electroless metal plating film 108 can be removed by using soft etching (flash etching) or the like. Here, the soft etching treatment can be performed, for example, by etching using an etchant containing sulfuric acid and hydrogen peroxide. Thereby, the metal layer 103 can be formed. The metal layer 103 is composed of the electroless metal plating film 108 and the electrolytic metal plating layer 109.

  Furthermore, a build-up layer can be laminated on the printed wiring board 100 as necessary, and multilayer connection can be made by repeating the steps of interlayer connection and circuit formation by a semi-additive process.

The printed wiring board 100 of this embodiment is obtained by the above.

[Semiconductor package]
Next, the semiconductor package 300 according to the present embodiment will be described. 7 and 8 are cross-sectional views showing an example of the configuration of the semiconductor package 300 according to the embodiment of the present invention. The printed wiring board 100 can be used in a semiconductor package 300 as shown in FIGS. A method for manufacturing the semiconductor package 300 is not particularly limited, and examples thereof include the following methods.

  First, build-up layers are stacked on the printed wiring board 100 as necessary, and the steps of interlayer connection and circuit formation by a semi-additive process are repeated. And the soldering resist layer 301 is laminated | stacked on the both surfaces or one side of the printed wiring board 100 as needed.

  The method for forming the solder resist layer 301 is not particularly limited. For example, a method of forming a dry film type solder resist by laminating and exposing and developing, or by exposing and developing a liquid resist printed This is done by the forming method.

  Subsequently, by performing a reflow process, the semiconductor element 307 is fixed to the connection terminal which is a part of the wiring pattern via the solder bump 310. Thereafter, the semiconductor element 307, the solder bump 310, and the like are sealed with a sealing material 313, whereby the semiconductor package 300 as shown in FIGS. 7 and 8 is obtained.

[Semiconductor device]
Next, the semiconductor device 400 according to the present embodiment will be described. 9 and 10 are cross-sectional views showing an example of the configuration of the semiconductor device 400 according to the embodiment of the present invention.
The printed wiring board 100 and the semiconductor package 300 can be used in a semiconductor device 400 as shown in FIGS. A method for manufacturing the semiconductor device 400 is not particularly limited, and examples thereof include the following methods.

  First, the semiconductor package 300 is manufactured using a printed wiring board provided with circuit layers on both sides. Here, the semiconductor element 307 is mounted only on one surface of the printed wiring board, and the solder resist layer 301 having an opening is provided on the other surface. A solder bump 310 is formed by applying a solder paste to the opening of the solder resist layer 301 of the obtained semiconductor package 300 and then mounting a solder ball, followed by a reflow process. The solder bump 310 can also be formed by attaching a solder ball prepared in advance to the opening.

  Next, the semiconductor package 300 is mounted on the mounting substrate 420 by joining the connection terminals 425 of the mounting substrate 420 and the solder bumps 310, and the semiconductor device 400 shown in FIGS. 9 and 10 is obtained.

  The semiconductor package 300 in this embodiment is less likely to warp and crack, and can be thinned. Therefore, the semiconductor device 400 including the semiconductor package 300 has excellent connection reliability.

  Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention. .

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these. In addition, in an Example, unless otherwise specified, a part represents a mass part. Moreover, each thickness is represented by the average film thickness.

Example 1
(1) Preparation of resin varnish (A) A naphthylene ether type epoxy resin represented by general formula (3) (manufactured by DIC, EPICLON HP-6000, in general formula (3), each R is a hydrogen atom, 30.0 parts by mass of a mixture of a component where n = 1 and a component where n = 2), and 10.0 parts by mass of a phenol novolac-type cyanate resin (LONZA, Primeset PT-30) which is a cyanate resin, 20.0 parts by mass of an elastomer-modified polyamide resin (aromatic polyamide resin, rubber component: butadiene-acrylonitrile copolymer, manufactured by Nippon Kayaku Co., Ltd., KAYAFLEX BPAM155), which is a thermoplastic resin, and 1-benzyl-2, which is a curing agent -0.3 part by mass of phenylimidazole (manufactured by Shikoku Kasei Co., Ltd., Curazole 1B2PZ), and dimethylaceto The mixture was added to a mixed solvent of imide and methyl ethyl ketone, and dissolved by stirring for 30 minutes.
Furthermore, epoxy silane coupling agent (Momentive Performance Materials Co., A187) 0.2 parts by mass as a coupling agent and silica nanoparticles (nanosilica, average particle size 56 nm) 39.5 mass as inorganic filler. And the mixture was stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish (A) having a solid content of 30% by weight.

(2) Preparation of metal foil with primer layer A resin varnish (A) was applied to one side of a 3 μm thick ultrathin copper foil (MT18SD-H, with a carrier copper foil of 18 μm thickness, manufactured by Mitsui Mining & Mining Co., Ltd.). Coating was performed using a coater apparatus so that the thickness of the primer layer after drying (after semi-curing) was 5 μm. This was dried with a dryer at 160 ° C. for 10 minutes to prepare a metal foil with a primer layer.

(3) Manufacture of double-sided copper-clad laminate The primer layers of the two metal foils with a primer layer obtained as described above are overlapped to face each other, and are heated at 200 ° C. and 30 kgf / mm ² using a hot press. Under the above pressing conditions, the primer layer was cured by heating and pressing for 1 hour. Thereby, the primer layers of the metal foil with a primer layer were bonded together, and the double-sided copper clad laminated board was produced.

(4) Preparation of resin varnish (B) 59.7 parts by mass of silica particles (manufactured by Admatechs, SO25R, average particle size 0.5 μm) and epoxy resin (Nippon Kayaku Co., Ltd., NC3000, biphenyl aralkyl type epoxy resin) , Weight average molecular weight: 1300, softening point: 57 ° C., epoxy equivalent: 276 g / eq) 11.2 parts by mass and cyanate resin (manufactured by LONZA, Primeset PT-30, phenol novolac type cyanate resin, weight average molecular weight 380) 20.0 parts by mass, 8.8 parts by mass of phenol resin (Maywa Kasei Co., Ltd., MEH7851) and 0.3 parts by mass of epoxy silane coupling agent (Momentive Performance Materials, A187) 70% by weight of solid content Of resin varnish (B) was obtained.

(5) Preparation of metal-clad laminate On the primer layer of the metal foil with primer layer obtained in (2), the resin varnish (B) is made to have a thickness of 19 μm using a comma coater device. Coated. This was dried with a 160 ° C. drying apparatus for 10 minutes to produce an insulating resin sheet with metal foil (semi-cured). Two similar insulating resin sheets with metal foil were prepared.
The obtained two insulating resin sheets with metal foil were respectively arranged on both sides of a fiber base material (thickness 48 μm, Nittobo E glass woven fabric, WEA-1280) so that the insulating resin layer was in contact with the fiber base material. The fiber base material was impregnated with each insulating resin layer by heating and pressing with a vacuum press under the conditions of a pressure of 0.5 MPa and a temperature of 140 ° C. for 1 minute. The total of the insulating resin layer and the fiber base material at this time was 60 μm.
Subsequently, it heat-press-molded for 2 hours at the pressure of 1 MPa and the temperature of 220 degreeC, and produced the metal-clad laminated board which has a copper foil with a carrier on both surfaces with a thickness of 112 micrometers.

(6) Fabrication of printed wiring board The carrier copper foil of the metal-clad laminate obtained in (5) was peeled off, and the ultrathin copper foil was removed by etching to expose the primer layer. Next, a through hole (through hole) was formed by a carbonic acid laser. Next, the inside of the through hole and the surface of the primer layer were immersed in an 80 ° C. swelling liquid (manufactured by Atotech Japan, Swelling Dip Securigant P) for 10 minutes, and further an 80 ° C. potassium permanganate aqueous solution (manufactured by Atotech Japan) , And concentrated for 5 minutes, and then neutralized and roughened.
After passing through the steps of degreasing, applying a catalyst, and activating this, electroless copper plating film is about 1 μm, plating resist formation, electroless copper plating film is used as a power feeding layer, and pattern electroplating copper is formed to form 12 μm L / S = 12 / 12 μm fine circuit processing was performed. Next, an annealing process was performed at 200 ° C. for 60 minutes with a hot air drying apparatus, and then the power feeding layer was removed by flash etching.
Next, a solder resist (manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR-4000 AUS703) is printed, exposed with a predetermined mask so that the semiconductor element mounting pads and the like are exposed, developed and cured, and the solder resist on the circuit The layer thickness was 12 μm.
Finally, on the circuit layer exposed from the solder resist layer, an electroless nickel plating layer of 3 μm and a plating layer of 0.1 μm of the electroless gold plating layer were further formed to obtain a printed wiring board. .

(7) Production of semiconductor package A semiconductor package is obtained by using a flip chip bonder device to obtain a semiconductor element (TEG chip, size 8 mm × 8 mm, thickness 0.1 mm) having solder bumps on the printed wiring board obtained in (6). It was mounted by thermocompression bonding. Next, after solder bumps were melt-bonded in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4152S) was filled, and then the liquid sealing resin was cured to obtain a semiconductor package. The liquid sealing resin was cured at a temperature of 150 ° C. for 120 minutes. As the solder bumps of the semiconductor element, those formed of eutectic of Sn / Pb composition were used. Finally, it was separated into pieces of 14 mm × 14 mm with a router to obtain a semiconductor package.

(8) Production of film with primer layer The resin varnish (A) obtained in (1) is a 38 μm thick polyethylene terephthalate film (Mitsubishi Chemical Polyester, SFB-38, 38 μm thick, width) as a carrier film. On one side of 480 m), coating was performed using a comma coater so that the primer layer after drying (after semi-curing) had a thickness of 5 μm. This was dried with a drying apparatus at 160 ° C. for 10 minutes to produce a film with a primer layer.

(9) Production of prepreg with primer layer On the primer layer of the film with primer layer obtained in (8), the resin varnish (B) is made to have a thickness of 19 μm using a comma coater device. Coated. This was dried with a 160 ° C. drying apparatus for 10 minutes to produce an insulating resin sheet (semi-cured) with a carrier film. Two similar insulating resin sheets with a carrier film (semi-cured) were prepared.
The obtained two insulating resin sheets with a carrier film are arranged on both sides of a fiber base material (thickness 48 μm, Nittobo E glass woven fabric, WEA-1280) so that the insulating resin layer is in contact with the fiber base material. The fiber base material was impregnated with each insulating resin layer by heating and pressing with a vacuum press at a pressure of 0.5 MPa and a temperature of 100 ° C. for 1 minute. The total of the insulating resin layer and the fiber base material at this time was 60 μm. The carrier film was peeled off to obtain a prepreg having a thickness of 70 μm.

(10) Linear expansion coefficient The metal foil of the double-sided copper-clad laminate obtained in (3) was removed by etching, and a 4 mm × 20 mm test piece was prepared from the primer layer from which the metal foil was removed. About this test piece, using a TMA (thermomechanical analysis) apparatus (TA Instrument Co., Ltd., Q400), a temperature range of 30 to 300 ° C., 10 ° C./min, and a load of 5 g, 50 to 50 in the second cycle. The linear expansion coefficient (CTE) in the plane direction (XY direction) at 150 ° C. was measured.

(11) Glass transition temperature The metal foil of the double-sided copper-clad laminate obtained in (3) was removed by etching, and a 6 mm × 25 mm test piece was prepared from the primer layer from which the metal foil was removed. About this test piece, it heated up at 5 degree-C / min (frequency 1Hz) using DMA apparatus (The dynamic viscoelasticity measuring apparatus DMA983 by TA Instruments), and made the peak position of tan-delta the glass transition temperature.

(12) Peel strength The copper foil is removed from the metal-clad laminate obtained in (5) by etching, and dipped in a swelling solution at 60 ° C. (Swelling Dip Securigant P, manufactured by Atotech Japan) for 10 minutes, and further 80 After immersion for 5 minutes in an aqueous potassium permanganate solution (manufactured by Atotech Japan Co., Ltd., Concentrate Compact CP) at 0 ° C., the mixture was neutralized and roughened.
After passing through the steps of degreasing, applying a catalyst, and activating this, an electroless copper plating film was formed to have a thickness of about 1 μm and electroplated copper was formed to 30 μm, and annealed at 200 ° C. for 60 minutes in a hot air drying apparatus. A 100 mm × 20 mm test piece was prepared based on JIS-C-6481, and the peel strength at 23 ° C. was measured.

(13) Evaluation of fine wiring processability The printed wiring board after forming a fine circuit pattern of L / S = 12/12 μm in (6) was evaluated by a thin wire appearance inspection and a continuity check with a laser microscope. The evaluation criteria are as follows.
◎: No problem in both shape and continuity ○: No short circuit or wire breakage, no problem ×: Short circuit, wire breakage

(14) Insulation reliability evaluation On the fine circuit pattern of L / S = 12/12 μm of the printed wiring board obtained in (6), a buildup material (BLA-3700GS manufactured by Sumitomo Bakelite Co., Ltd.) is used instead of the solder resist. A test sample was prepared by laminating and curing. Using this test sample, the continuous humidity 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 10 ⁶ Ω or less was regarded as a failure. The evaluation criteria are as follows.
◎: No failure for 300 hours or more ○: Failure for 150 hours or more and less than 300 hours ×: Failure for less than 150 hours

(15) Warpage evaluation of semiconductor package Warpage of the semiconductor package obtained in (7) at normal temperature (23 ° C.) and 260 ° C. is measured using a temperature variable laser three-dimensional measuring machine (manufactured by Hitachi Technology and Service, model LS220-MT100MT50). Was used to evaluate. The semiconductor element surface was placed in the sample chamber of the measuring machine, the displacement in the height direction was measured, and the largest value of the displacement difference was taken as the amount of warpage. The evaluation criteria are as follows.
Normal temperature (23 ℃)
A: Warpage amount is less than 150 μm B: Warpage amount is 150 μm or more and less than 200 μm ×: Warpage amount is 200 μm or more and 260 ° C.
A: Warpage amount is less than 100 μm B: Warpage amount is 100 μm or more and less than 150 μm ×: Warpage amount is 150 μm or more

(16) Observation of sea-island structure of primer layer The copper foil of the double-sided copper-clad laminate obtained in (3) was removed by etching, and then the resin component was dyed by a ruthenic acid dyeing method. A section sample of 100 μm × 100 μm was cut out and observed with a transmission electron microscope (H-7100FA, manufactured by Hitachi) at an acceleration voltage of 100 kV and a magnification of 10,000 to 40,000 times. The case where the sea-island structure is formed is marked with ◯, and the case where the sea-island structure is not marked with ×. Moreover, a part was cut out from the sea phase and the island phase, and the resin contained in each phase was analyzed by gas chromatography.

(Example 2)
Example 1 except that a polyamide-imide resin (HR-11NN manufactured by Toyobo Co., Ltd.) was used instead of the elastomer-modified polyamide resin (aromatic polyamide resin, manufactured by Nippon Kayaku Co., Ltd., KAYAFLEX BPAM155) used for the resin varnish (A). And so on.

Example 3
Example 1 except that a polyamide-imide resin (HR-16NN manufactured by Toyobo Co., Ltd.) was used instead of the elastomer-modified polyamide resin (aromatic polyamide resin, manufactured by Nippon Kayaku Co., Ltd., KAYAFLEX BPAM155) used for the resin varnish (A). And so on.

Example 4
Example 1 except that a polyamide-imide resin (V-8000, manufactured by DIC) was used instead of the elastomer-modified polyamide resin (aromatic polyamide resin, manufactured by Nippon Kayaku Co., Ltd., KAYAFLEX BPAM155) used for the resin varnish (A). The same was done.

(Example 5)
Example 1 except that a polyethersulfone resin (5003P manufactured by Sumitomo Chemical Co., Ltd.) was used instead of the elastomer-modified polyamide resin (aromatic polyamide resin, manufactured by Nippon Kayaku Co., Ltd., KAYAFLEX BPAM155) used for the resin varnish (A). The same was done.

(Synthesis example 1) Cyanate resin (naphthol aralkyl type cyanate resin)
A naphthol aralkyl type phenolic resin (manufactured by Nippon Steel Chemical Co., Ltd., SN485N, hydroxyl group equivalent: 215 g / eq) (101 g, 0.47 mol hydroxyl group) was charged in 400 g of methyl isobutyl ketone (hereinafter MIBK) and dissolved at room temperature with stirring. After dissolution, it was cooled to -10 ° C. At −10 ° C., 110 g of cyanogen bromide (hereinafter BrCN) was added (purity 95%, 0.987 mol), and when the internal temperature reached −15 ° C., 100 g (0.99 mol) of triethylamine (hereinafter TEA) and 600 g of MIBK The mixture was added dropwise over 1 hour. After dropping, the reaction was further aged for 30 minutes and further aged for about 2 hours to complete the reaction.
To the obtained solution, 400 ml of pure water was added for liquid separation, and further 1000 ml of 5% aqueous hydrogen chloride solution (HCl) was added for liquid separation. Furthermore, it was washed and separated twice with 500 g of 10% saline and washed twice with 500 ml of pure water.
The organic layer was dehydrated with anhydrous sodium sulfate, and then the solvent was removed under reduced pressure to obtain a solid resin. The obtained solid was washed with hexane and then dried under reduced pressure to obtain a naphthol aralkyl-type cyanate resin. The naphthol aralkyl-type cyanate resin thus obtained was analyzed by infrared absorption spectrum measurement (IR Prestige-21, KBr transmission method manufactured by Shimadzu Corporation), and 3200 to 3600 cm ⁻¹ which is an absorption band of a phenolic hydroxyl group. The peak of 2264 cm ^−1, which is the absorption band of nitrile cyanate ester, was confirmed.

(Example 6)
The same procedure as in Example 1 was conducted except that the cyanate resin of Synthesis Example 1 was used instead of the phenol novolac-type cyanate resin (LONZA, Primaset PT-30) used for the resin varnish (A).

(Example 7)
The same procedure as in Example 1 was conducted except that the following resin varnish was used instead of the resin varnish (A).
29.3 parts by mass of an epoxy resin naphthylene ether type epoxy resin (DIC Corporation, EPICLON HP-6000) and tetrafunctional naphthalene type epoxy resin (DIC Corporation, EPICLON HP-4710) 10.0 parts by mass; 20.0 parts by mass of an elastomer-modified polyamide resin (aromatic polyamide resin, manufactured by Nippon Kayaku Co., Ltd., KAYAFLEX BPAM155), which is a thermoplastic resin, and 1-benzyl-2-phenylimidazole (cured by Shikoku Kasei Co., Ltd.), which is a curing agent 1B2PZ) and 1.0 part by mass were added to a mixed solvent of dimethylacetamide and methyl ethyl ketone and stirred for 30 minutes to dissolve.
Furthermore, epoxy silane coupling agent (Momentive Performance Materials Co., A187) 0.2 parts by mass as a coupling agent, silica nanoparticles (nanosilica, average particle size 56 nm) as an inorganic filler 39.5 parts by mass And stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 30%.

(Example 8)
The same procedure as in Example 1 was conducted except that the following resin varnish was used instead of the resin varnish (A).
29.3 parts by mass of an epoxy resin, naphthylene ether type epoxy resin (manufactured by DIC, EPICLON HP-6000) and bismaleimide (manufactured by Daiwa Kasei Co., Ltd., 4,4′-diphenylmethane bismaleimide BMI-1000) 10.0 20.0 parts by mass of an elastomer-modified polyamide resin (aromatic polyamide resin, manufactured by Nippon Kayaku Co., Ltd., KAYAFLEX BPAM155) as a thermoplastic resin, and 1-benzyl-2-phenylimidazole (Shikoku Chemicals) as a curing agent 1.0 part by mass (Corazole 1B2PZ) manufactured by the company was added to a mixed solvent of dimethylacetamide and methyl ethyl ketone and dissolved by stirring for 30 minutes.
Furthermore, 0.29.5 parts by mass of an epoxy silane coupling agent (Momentive Performance Materials Co., A187), which is a coupling agent, and 39.5 parts by mass of silica nanoparticles (nanosilica, average particle size 56 nm) as an inorganic filler The mixture was added and stirred for 10 minutes using a high-speed stirrer to prepare a resin varnish having a solid content of 30%.

(Comparative Example 1)
The biphenylaralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) was used without using the naphthylene ether type epoxy resin (DIC Corporation, EPICLON HP-6000) used for the resin varnish (A). Same as Example 1.

(Comparative Example 2)
Except for using naphthalene diol epoxy resin (DIC Corporation, EPICLON HP-4032D) without using naphthylene ether type epoxy resin (DIC Corporation, EPICLON HP-6000) used for resin varnish (A). Same as Example 1.

(Comparative Example 3)
Example 8 except that a biphenylaralkyl type epoxy resin (Nippon Kayaku Co., Ltd., NC-3000) was used without using the naphthylene ether type epoxy resin (DICIC, EPICLON HP-6000) used for the resin varnish. And so on.

(Comparative Example 4)
The same procedure as in Example 1 was conducted except that the following resin varnish was used instead of the resin varnish (A).
40.0 parts by mass of naphthylene ether type epoxy resin (EPICLON HP-6000, manufactured by DIC) which is an epoxy resin, and 20.0 mass parts of phenol novolac type cyanate resin (LONZA, Primase PT-30) which is a cyanate resin. And 0.3 parts by mass of 1-benzyl-2-phenylimidazole (Curesol 1B2PZ, Shikoku Kasei Co., Ltd.), which is a curing agent, are added to a mixed solvent of dimethylacetamide and methyl ethyl ketone and dissolved by stirring for 30 minutes. It was.
Further, 0.2 parts by mass of an epoxysilane coupling agent (M187, manufactured by Momentive Performance Materials, Inc., A187) is added as a coupling agent, and 39.5 parts by mass of silica nanoparticles (nanosilica, average particle size 56 nm) is added as an inorganic filler. And it stirred for 10 minutes using the high-speed stirring apparatus, and prepared the resin varnish of 30% of solid content.

  The results are shown in Table 1. All of the primer layers of Examples 1 to 8 formed a sea-island structure, and naphthylene ether type epoxy resin was detected from the sea phase, and thermoplastic resin was detected from the island phase.

DESCRIPTION OF SYMBOLS 100 Printed wiring board 101 Insulating layer 103 Metal layer 105 Primer layer 107 Via hole 108 Electroless metal plating film 109 Electrolytic metal plating layer 111 Core layer 117 Buildup layer 200 Prepreg with primer layer 201 Fiber base material 203 Resin layer 205 Plating resist 210 Prepreg 250 Metal foil with primer layer 255 Metal foil 280 Metal-clad laminate 300 Semiconductor package 301 Solder resist layer 307 Semiconductor element 310 Solder bump 313 Sealant 400 Semiconductor device 420 Mounting substrate 425 Connection terminal

Claims (17)

A resin composition for forming a primer layer, which is used to form a primer layer that is interposed between an insulating layer and a metal layer and causes the insulating layer and the metal layer to adhere to each other,
A naphthylene ether type epoxy resin represented by the following general formula (1);
A thermoplastic resin;
An inorganic filler;
A resin composition for forming a primer layer.

(In the general formula (1), n is an integer of 1 or more and 20 or less, l is an integer of 1 or 2, and R ₁ is independently a hydrogen atom, a benzyl group, an alkyl group, or the following general formula ( 2), and each R ₂ is independently a hydrogen atom or a methyl group.)

(In the general formula (2), Ar is each independently a phenylene group or a naphthylene group, R ₂ is each independently a hydrogen atom or a methyl group, and m is an integer of 1 or 2.) In the primer layer forming resin composition according to claim 1,
A resin composition for forming a primer layer, wherein the insulating layer and the metal layer constitute a part of a printed wiring board. The resin composition for forming a primer layer according to claim 1 or 2,
A resin composition for forming a primer layer, wherein the metal layer is a circuit layer. In the resin composition for primer layer formation as described in any one of Claims 1 thru | or 3,
The primer layer formed by the primer layer forming resin composition has a sea-island structure,
A resin composition for forming a primer layer, wherein at least the naphthylene ether type epoxy resin is present in a sea phase and the thermoplastic resin is present in an island phase. In the resin composition for primer layer formation as described in any one of Claims 1 thru | or 4,
A resin composition for forming a primer layer, wherein the thermoplastic resin contains a rubber component. In the resin composition for primer layer formation as described in any one of Claims 1 thru | or 5,
A resin composition for forming a primer layer, wherein the thermoplastic resin is one or two or more resins selected from the group consisting of a polyamide resin, a thermoplastic polyimide resin, a polyamideimide resin, and a polyethersulfone resin. In the resin composition for primer layer formation as described in any one of Claims 1 thru | or 6,
A resin composition for forming a primer layer, wherein the inorganic filler contains silica nanoparticles. In the resin composition for primer layer formation as described in any one of Claims 1 thru | or 7,
Furthermore, the resin composition for primer layer formation containing a coupling agent. In the resin composition for primer layer formation as described in any one of Claims 1 thru | or 8,
The primer layer-forming resin composition is a primer layer-forming resin composition used for a printed wiring board for forming a circuit by a semi-additive process method. In the resin composition for forming a primer layer according to claim 9,
The primer layer-forming resin formed using the primer layer-forming resin composition is formed between the insulating layer and the metal layer in at least one of the core layer and the build-up layer. Composition. In the resin composition for primer layer formation as described in any one of Claims 1 thru | or 10,
The resin composition for primer layer formation whose glass transition temperature by the dynamic viscoelasticity measurement of the hardened | cured material obtained by heat-curing the said resin composition for primer layer formation at 200 degreeC for 1 hour is 150 to 250 degreeC. In the resin composition for primer layer formation as described in any one of Claims 1 thru | or 11,
A resin composition for forming a primer layer, wherein a linear expansion coefficient of a cured product obtained by heating and curing the primer layer-forming resin composition at 200 ° C. for 1 hour is 75 ppm / ° C. or less. A prepreg formed by impregnating at least one layer of a fiber base material with a resin composition containing a thermosetting resin and an inorganic filler;
A primer layer that is interposed between the metal layer formed on at least one surface of the prepreg and the prepreg, and causes the metal layer and the prepreg to adhere to each other;
A prepreg with a primer layer,
A prepreg with a primer layer, wherein the primer layer is formed using the primer layer forming resin composition according to any one of claims 1 to 12. Metal foil,
A primer layer formed on at least one surface of the metal foil;
A metal foil with a primer layer,
A metal foil with a primer layer, wherein the primer layer is formed using the primer layer forming resin composition according to any one of claims 1 to 12. An insulating layer comprising a thermosetting resin, an inorganic filler and a fiber substrate;
Metal foil laminated on both sides or one side of the insulating layer;
A primer layer having a thickness smaller than the thickness of the insulating layer, and interposing between the insulating layer and the metal foil to adhere the insulating layer and the metal foil,
A metal-clad laminate having
A metal-clad laminate, wherein the primer layer is formed using the resin composition for forming a primer layer according to any one of claims 1 to 12.   A printed wiring board obtained by processing a circuit on the metal-clad laminate according to claim 15.   A semiconductor package formed by mounting a semiconductor element on the printed wiring board according to claim 16.

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