CN117885412A

CN117885412A - Resin sheet with metal foil

Info

Publication number: CN117885412A
Application number: CN202311309289.0A
Authority: CN
Inventors: 渡边真俊
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2022-10-13
Filing date: 2023-10-10
Publication date: 2024-04-16
Also published as: KR20240051842A; JP2024057908A

Abstract

The invention provides a resin sheet with metal foil, etc. capable of obtaining a cured product with low linear thermal expansion coefficient, wherein the generation of expansion is suppressed. The solution of the present invention is a resin sheet with a metal foil, comprising: the metal foil comprises a metal foil having a first surface, and a resin composition layer bonded to the first surface of the metal foil, wherein the maximum height roughness (Rz) of the first surface of the metal foil is 1000nm or more, the resin composition layer contains (A) an inorganic filler, and when the nonvolatile content of the resin composition layer is 100 mass%, the content of the (A) inorganic filler is 40 mass% or more and 80 mass% or less, the melt viscosity of the resin composition layer at 90 ℃ is 5000 poise or more and 100000 poise or less, and the peel strength between the metal foil and the resin composition layer is 0.01kgf/cm or more and 0.3kgf/cm or less.

Description

Resin sheet with metal foil

Technical Field

The present invention relates to a resin sheet with a metal foil. The present invention also relates to a circuit board manufactured using the resin sheet with a metal foil, and a semiconductor device including the circuit board.

Background

Circuit boards such as printed wiring boards, which are widely used in various electronic devices, are required to be thin in layers and fine in wiring of circuits in order to miniaturize and highly functionalize the electronic devices. As a technique for manufacturing a circuit board, a manufacturing method using a build-up (build-up) method in which insulating layers and conductor layers (wiring layers) are alternately stacked is known. In the manufacturing method based on the stacking method, the insulating layer is generally formed by thermally curing a resin composition layer in a resin sheet, and the conductor layer is formed by a technique such as a half additive method (SAP), a modified half additive Method (MSAP), a subtractive method (subtractive method), or the like.

In recent years, as a method of forming a conductor layer on an insulating layer, a method of using a resin sheet with a metal foil and using the metal foil as a conductor layer has been proposed. (for example, refer to patent documents 1 and 2).

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2022-43685

Patent document 2: japanese patent application laid-open No. 2010-161497.

Disclosure of Invention

Problems to be solved by the invention

The resin sheet with a metal foil is usually produced by bonding a resin composition layer to a metal foil. This bonding is usually performed under basic heating conditions at atmospheric pressure, but air existing at the interface between the metal foil and the resin composition layer cannot be removed due to the bonding conditions or the properties of the resin composition layer, and voids (void) may be generated. If voids are generated, expansion occurs between the conductor layer and the insulating layer when the resin composition layer is cured.

In order to suppress the generation of voids, a method of reducing the content of the inorganic filler contained in the resin composition layer to reduce the melt viscosity of the resin composition layer may be considered.

However, if the content of the inorganic filler is reduced, the linear Coefficient of Thermal Expansion (CTE) of the insulating layer becomes high. If the linear thermal expansion coefficient is high, the insulating layer may expand or contract repeatedly with a temperature change, and cracks may be generated due to deformation thereof.

The present invention has been made in view of the above problems, and an object thereof is to provide: a resin sheet with a metal foil, which can obtain a cured product having a low linear thermal expansion coefficient with suppressed generation of expansion; a circuit board manufactured using the resin sheet with a metal foil; a semiconductor device provided with the circuit board.

Means for solving the problems

The present inventors have conducted intensive studies and as a result found that: a resin sheet with a metal foil, the resin sheet with a metal foil comprising: the metal foil having the first surface and the resin composition layer bonded to the first surface of the metal foil are adjusted so that the melt viscosity of the first surface of the metal foil and the resin composition layer at 90 ℃, the content of the inorganic filler contained in the resin composition layer, and the peel strength between the metal foil and the resin composition layer are within predetermined ranges. As a result, they have found that a cured product having a low linear thermal expansion coefficient with suppressed expansion can be obtained, and completed the present invention.

Namely, the present invention includes the following:

[1] a resin sheet with a metal foil, the resin sheet with a metal foil comprising:

metal foil having a first face, and

a resin composition layer bonded to the first surface of the metal foil,

the maximum height roughness (Rz) of the first surface of the metal foil is 1000nm or more,

the resin composition layer contains (A) an inorganic filler,

when the nonvolatile content of the resin composition layer is set to 100 mass%, the content of the inorganic filler (A) is 40 mass% or more and 80 mass% or less,

the melt viscosity of the resin composition layer at 90 ℃ is 5000 poise or more and 100000 poise or less,

the peel strength between the metal foil and the resin composition layer is 0.01kgf/cm or more and 0.3kgf/cm or less;

[2] the resin sheet with a metal foil according to [1], wherein a void formed continuously is provided at an interface between the first surface of the metal foil and the resin composition layer;

[3] the resin sheet with a metal foil according to [1] or [2], wherein the resin composition layer contains (B) an epoxy resin;

[4] the resin sheet with a metal foil according to any one of [1] to [3], wherein the resin composition layer contains (C) a curing agent;

[5] the resin sheet with a metal foil according to any one of [1] to [4], wherein a linear thermal expansion coefficient of a cured product of the resin composition layer is 40ppm/°c or less;

[6] The resin sheet with a metal foil according to any one of [1] to [5], wherein a protective film is provided on a surface of the resin composition layer which is not joined to the metal foil;

[7] the resin sheet with a metal foil according to [6], wherein the protective film is subjected to a mold release treatment;

[8] the resin sheet with a metal foil according to any one of [1] to [7], wherein the metal foil is a copper foil;

[9] a circuit substrate, comprising: an insulating layer formed using a cured product of the resin composition layer of the resin sheet with a metal foil according to any one of [1] to [8], and a conductor layer formed using a metal foil of the resin sheet with a metal foil according to any one of [1] to [8 ];

[10] a semiconductor device comprising the circuit substrate of [9 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there may be provided: a resin sheet with a metal foil, which can obtain a cured product having a low linear thermal expansion coefficient with suppressed generation of expansion; a circuit board manufactured using the resin sheet with a metal foil and a semiconductor device provided with the circuit board.

Drawings

Fig. 1 is a schematic cross-sectional view showing an example of a resin sheet with a metal foil according to the present invention.

Detailed Description

Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be implemented with any modifications within the scope of the claims and the equivalents thereof.

[ resin sheet with Metal foil ]

The resin sheet with a metal foil of the present invention comprises: the metal foil comprises a metal foil having a first surface, and a resin composition layer bonded to the first surface of the metal foil, wherein the maximum height roughness (Rz) of the first surface of the metal foil is 1000nm or more, the resin composition layer contains (A) an inorganic filler, and when the nonvolatile content of the resin composition layer is 100 mass%, the content of the (A) inorganic filler is 40 mass% or more and 80 mass% or less, the melt viscosity of the resin composition layer at 90 ℃ is 5000 poise or more and 100000 poise or less, and the peel strength between the metal foil and the resin composition layer is 0.01kgf/cm or more and 0.3kgf/cm or less. By using such a resin sheet with a metal foil, a cured product which can suppress the occurrence of swelling can be obtained.

Fig. 1 is a schematic cross-sectional view of an example of a resin sheet with a metal foil according to the present invention. The resin sheet with metal foil 1 includes: a metal foil 2 having a first face 2a and a resin composition layer 3. The resin composition layer 3 is bonded to the first surface 2a of the metal foil 2. The resin sheet 1 with a metal foil may contain a protective film 4 on the surface of the resin composition layer 3 that is not joined to the metal foil 2.

Since the maximum height roughness (Rz) of the first surface 2a of the metal foil 2 is 1000nm or more, a plurality of fine protrusions 21 are continuously formed on the entire first surface 2 a. That is, innumerable irregularities are formed on the entire first surface 2 a. In the resin sheet 1 with a metal foil, the metal foil 2 and the resin composition layer 3 are bonded under the condition that the peel strength between the metal foil 2 and the resin composition layer 3 is 0.01kgf/cm or more and 0.3kgf/cm or less. If the metal foil 2 and the resin composition layer 3 are bonded under the condition that the peel strength between the metal foil 2 and the resin composition layer 3 is 0.01kgf/cm or more and 0.3kgf/cm or less when the melt viscosity of the resin composition layer 3 is 5000 poise or more and 100000 poise or less at 90 ℃, the protrusions 21 of the first surface 2a are not bonded so as to be entirely embedded in the resin composition layer 3, but rather, a part of the protrusions 21 is embedded in the resin composition layer 3. Therefore, the metal foil 2 and the resin composition layer 3 have voids 22 continuously formed between the protrusions 21 at the interface therebetween. The void 22 is formed continuously in the in-plane direction perpendicular to the thickness direction, and can communicate with the external space.

When a circuit board is formed using a resin sheet with a metal foil, a resin composition layer of the resin sheet with a metal foil is laminated to an inner layer board by a vacuum hot press treatment. Since the conventional resin sheet with a metal foil does not have the void 22 between the metal foil 2 and the resin composition layer 3 unlike the resin sheet with a metal foil 1 of the present invention, there is no escape of the void (air) even when the vacuum hot press treatment is performed, and therefore, expansion occurs in the cured product of the resin composition layer. As described above, in the conventional resin sheet with a metal foil, it is necessary to reduce the content of the inorganic filler contained in the resin composition layer and to reduce the melt viscosity of the resin composition layer in order to suppress the occurrence of voids. Therefore, the linear thermal expansion coefficient of the insulating layer becomes high.

In contrast, the resin sheet with metal foil 1 of the present invention has the voids 22, and the voids 22 are formed continuously between the protrusions 21. As a result, air in the voids can be removed under vacuum conditions in the vacuum hot press treatment, and a cured product in which the occurrence of expansion is suppressed can be obtained. In addition, the resin sheet with metal foil 1 of the present invention has the voids 22, and therefore it is not necessary to reduce the melt viscosity of the resin composition layer 3. Therefore, it is not necessary to reduce the content of the inorganic filler contained in the resin composition layer, so that the linear thermal expansion coefficient of the insulating layer can be further reduced. In addition, the resin sheet with a metal foil of the present invention can generally obtain a cured product of a resin composition layer having a high glass transition temperature (Tg).

The maximum height roughness (Rz) of the first surface of the metal foil is 1000nm or more, preferably 2000nm or more, more preferably 3000nm or more, still more preferably 4000nm or more, 4500nm or more, from the viewpoint of obtaining a cured product in which the occurrence of expansion is suppressed. The upper limit is preferably 20000nm or less, more preferably 15000nm or less, still more preferably 10000nm or less, 8000nm or less. The maximum height roughness (Rz) can be measured by the method described in examples described later.

In the resin sheet with a metal foil, the peel strength between the metal foil and the resin composition layer is 0.01kgf/cm or more, preferably 0.015kgf/cm or more, and more preferably 0.02kgf/cm or more, from the viewpoint of obtaining a cured product having a low linear thermal expansion coefficient, in which the occurrence of expansion is suppressed. The upper limit is 0.3kgf/cm or less, preferably 0.25kgf/cm or less, and more preferably 0.2kgf/cm or less. The peel strength can be measured by the method described in examples described below.

The melt viscosity of the resin composition layer at 90℃is 5000 poise or more, preferably 10000 poise or more, and more preferably 15000 poise or more, from the viewpoint of obtaining a cured product having a low linear thermal expansion coefficient. The upper limit is 100000 poise or less, preferably 75000 poise or less, more preferably 50000 poise or less. Melt viscosity can be measured by the method described in examples described below.

< Metal foil >)

The resin sheet with a metal foil of the present invention has a metal foil. The conductor layer of the circuit substrate may be formed of a metal foil.

Examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil formed of a single metal of copper or a foil formed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

The metal foil may have a single-layer structure or a multilayer structure in which 2 or more single metal layers or alloy layers made of different types of metals or alloys are stacked. Examples of the metal foil having a multilayer structure include a carrier metal foil and an extremely thin metal foil bonded to the carrier metal foil. The metal foil of the multilayer structure may include a peeling layer capable of peeling the extremely thin metal foil from the carrier metal foil between the carrier metal foil and the extremely thin metal foil. The release layer is not particularly limited as long as it can release an extremely thin metal foil from a carrier metal foil, and examples thereof include an alloy layer of an element selected from Cr, ni, co, fe, mo, ti, W and P; an organic coating, and the like. When a metal foil having a multilayer structure is used, the resin composition layer is provided on the extremely thin metal foil.

From the viewpoint of remarkably obtaining the effect of the present invention, the thickness of the metal foil is preferably 1 μm or more, more preferably 1.5 μm or more, and even more preferably 2 μm or more. The upper limit is not particularly limited, but is preferably 35 μm or less, more preferably 25 μm or less, and still more preferably 15 μm or less. When the metal foil has a multilayer structure, the thickness of the entire metal foil is preferably in a range, and the thickness of the extremely thin metal foil may be, for example, in a range of 0.1 μm or more and 10 μm or less.

The method for producing the metal foil is not particularly limited as long as a predetermined maximum height roughness (Rz) can be obtained. The metal foil can be produced by a known method such as an electrolytic method or a rolling method.

The arithmetic average roughness (Ra) of the first surface of the metal foil is preferably 300nm or more, more preferably 350nm or more, still more preferably 400nm or more, and still more preferably 500nm or more, from the viewpoint of improving adhesion to the resin composition layer. The upper limit is not particularly limited, but is preferably 1000nm or less, more preferably 900nm or less, and still more preferably 800nm or less. The arithmetic average roughness (Ra) is a value measured according to ISO 25178, and may be measured using a non-contact surface roughness meter. Examples of the noncontact surface roughness meter include "WYKO NT3300" manufactured by VEECO INSTRUMENTS.

The metal foil may be commercially available. Examples of the commercial products of the metal foil include: "Micro Thin MT18Ex" from Mitsui metal mining company, "Micro Thin MT18FL" from Mitsui metal mining company, "3EC-III" from Mitsui metal mining company, "3EC-M3-VLP" from Mitsui metal mining company, "JDLC" from JX metal mining company, "JTCSLC" from JDLC "from Mitsui metal mining company," HA "from Mitsui metal foil powder industry, and" CF-TX4-SV "from Fund metal foil powder industry, V9" from Fund metal foil powder industry, HD "from Futf" from Fuff, RCF-T4X "from Fuff-T5B" from Fund metal mining company, etc.

< resin composition layer >

The resin sheet with a metal foil has a resin composition layer. The resin composition layer has a thermosetting function.

From the viewpoint of reducing the linear thermal expansion coefficient, the component contained in the resin composition layer contains (a) an inorganic filler. The resin composition layer may contain (B) an epoxy resin, (C) a curing agent, (D) a radical polymerizable compound, (E) a curing accelerator, (F) a thermoplastic resin, and (G) other additives, as necessary.

(A) Inorganic filler

The resin composition layer contains an inorganic filler as the component (A). By using the resin composition layer containing the component (A), a cured product having a low linear thermal expansion coefficient can be obtained.

(A) The inorganic filler is contained in the resin composition layer in the form of particles. As the material of the inorganic filler (a), an inorganic compound can be used. Examples of the material of the inorganic filler (a) include: silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, and the like. Among them, silica is particularly preferable. Examples of the silica include: amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. In addition, spherical silica is preferable as silica. (A) The inorganic filler may be used alone in 1 kind, or may be used in combination in an arbitrary ratio of 2 or more kinds.

Examples of the commercial products of the inorganic filler (a) include: "SP60-05", "SP507-05" manufactured by Nissan chemical materials Co., ltd; "YC100C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", manufactured by Admatechs; "UFP-30", "DAW-03", "FB-105FD" manufactured by Denka corporation; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama Co., ltd; "CellSpheres", "MGH-005" manufactured by Pacific Cement Co., ltd; and "eyebox", "BA-1" manufactured by diw catalyst chemical company.

(A) The average particle diameter of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, further preferably 3 μm or less, further more preferably 2 μm or less, and particularly preferably 1.5 μm or less. (A) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. (A) The average particle size of the inorganic filler material can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced by a laser diffraction scattering particle size distribution measuring apparatus on a volume basis, and the median particle size can be measured as the average particle size. As a measurement sample, a sample obtained by weighing 100mg of an inorganic filler and 10g of methyl ethyl ketone in a vial and dispersing the mixture with ultrasonic waves for 10 minutes was used. The measurement sample was measured for volume-based particle size distribution of the inorganic filler by a flow cell (flow cell) method using a laser diffraction type particle size distribution measuring device, the wavelength of the light source was set to blue and red, and the average particle size was calculated from the obtained particle size distribution as the median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, inc.

(A) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1m ² Preferably at least 0.5m ² Preferably 1m or more, and more preferably 1m ² Preferably 3m or more per gram ² And/g. (A) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100m ² Preferably less than or equal to/g, more preferably 70m ² Preferably 50m or less per gram ² Preferably less than or equal to/g, more preferably 30m ² Preferably less than or equal to/g, particularly preferably 10m ² And/g or less. The specific surface area of the inorganic filler was obtained by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech corporation) according to the BET method, and calculating the specific surface area using the BET multipoint method.

From the viewpoint of improving moisture resistance and dispersibility, (a) the inorganic filler is preferably treated with a surface treatment agent. Examples of the surface treatment agent include: fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, alkoxysilanes, organosilane-nitrogen compounds, titanate coupling agents, and the like. The surface treatment agent may be used alone or in combination of 1 or more than 2 kinds.

Examples of the commercial product of the surface treatment agent include: "KBM403" from Xinyue chemical industry Co., ltd. (3-glycidoxypropyl trimethoxysilane), "KBM803" from Xinyue chemical industry Co., ltd. (3-mercaptopropyl trimethoxysilane), "KBE903" from Xinyue chemical industry Co., ltd. (3-aminopropyl triethoxysilane), "KBM573" from Xinyue chemical industry Co., ltd. (hexamethyldisilazane), "KBM103" from Xinyue chemical industry Co., ltd. (phenyl trimethoxysilane), "KBM-4803" from Xinyue chemical industry Co., ltd. (long chain epoxy type silane coupling agent), and "KBM-7103" from Xinyue chemical industry Co., ltd. (3, 3-trifluoropropyl trimethoxysilane) and the like.

The degree of the surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, the inorganic filler is preferably surface-treated with 0.2 to 5 mass% of a surface-treating agent, more preferably 0.2 to 3 mass%, and even more preferably 0.3 to 2 mass%.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon amount per unit surface area of the inorganic filler is preferably 0.02mg/m ² The above is more preferably 0.1mg/m ² The above is more preferably 0.2mg/m ² The above. On the other hand, from the viewpoint of preventing an increase in melt viscosity of the resin composition layer or in melt viscosity in sheet form, it is preferably 1.0mg/m ² Hereinafter, more preferably 0.8mg/m ² Hereinafter, it is more preferably 0.5mg/m ² The following is given.

(A) Specifically, a sufficient amount of MEK is added as a solvent to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25℃for 5 minutes, the supernatant is removed, and the solid content is dried, and then the carbon amount per unit surface area of the inorganic filler can be measured by using a carbon analyzer.

When the nonvolatile component in the resin composition layer is 100 mass% from the viewpoint of obtaining a cured product having a low linear thermal expansion coefficient, the content of the inorganic filler (a) is 40 mass% or more, preferably 50 mass% or more, and more preferably 55 mass% or more. The upper limit is 80 mass% or less, preferably 75 mass% or less.

In the present invention, unless otherwise specified, the content of each component in the resin composition layer is a value obtained by setting the nonvolatile component in the resin composition layer to 100 mass%, and the nonvolatile component refers to the entire nonvolatile component after removal of the solvent in the resin composition layer.

(B) Epoxy resin

The resin composition layer may contain (B) an epoxy resin in combination with the component (a). (B) The epoxy resin may be used alone or in combination of 2 or more.

(B) Examples of the epoxy resin include: a bisxylenol (bispyrinol) type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a naphthol novolac (naptholac) type epoxy resin, a phenol novolac (phenol novolac) type epoxy resin, a tert-butyl catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidol amine type epoxy resin, a glycidol ester type epoxy resin, a glycidol cyclohexane type epoxy resin, a cresol novolac (cresol novolac) type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, a cycloaliphatic epoxy resin, a heterocyclic type epoxy resin, a spiro-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a naphthylene ether type epoxy resin, a triphenol type epoxy resin, a tetraphenyl ethane type epoxy resin, a phenol benzopyrrolidone (phthalone) type epoxy resin, and the like.

The resin composition layer preferably contains an epoxy resin having 2 or more epoxy groups in 1 molecule as the component (B). From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, relative to 100% by mass of the (B) epoxy resin.

The epoxy resin includes an epoxy resin that is liquid at a temperature of 20 ℃ (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20 ℃ (hereinafter sometimes referred to as "solid epoxy resin"). The resin composition layer may contain only a liquid epoxy resin or only a solid epoxy resin as the component (B), and preferably contains a liquid epoxy resin and a solid epoxy resin in combination.

As the liquid epoxy resin, a liquid epoxy resin having 2 or more epoxy groups in 1 molecule is preferable.

The liquid epoxy resin is preferably bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure, glycidyl cyclohexane type epoxy resin, phenol benzopyrrolone type epoxy resin, more preferably bisphenol a type epoxy resin, or alicyclic epoxy resin.

Specific examples of the liquid epoxy resin include: "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "jER828EL", "825", "EPIKOTE 828EL" by Mitsubishi chemical corporation (bisphenol A type epoxy resin); "jER807", "1750" manufactured by mitsubishi chemical company (bisphenol F type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical company; "630", "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi chemical corporation; "ZX1059" manufactured by Nissan chemical materials Co., ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., ltd; "CELLOXIDE 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by macrocellulite corporation; "PB-3600" manufactured by Daxiu corporation (epoxy resin having a butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane type epoxy resin) manufactured by Nissan chemical materials Co., ltd. The number of these may be 1 alone or 2 or more.

The solid epoxy resin is preferably a solid epoxy resin having 2 or more epoxy groups in 1 molecule, more preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and even more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.

The solid epoxy resin is preferably a binaphthol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene-ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol AF-type epoxy resin, or a tetraphenylethane-type epoxy resin, and more preferably a biphenyl-type epoxy resin, a naphthylene-ether-type epoxy resin, a naphthalene-type epoxy resin, or a binaphthol-type epoxy resin.

Specific examples of the solid epoxy resin include: "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4S", "HP6000L" (naphthalene ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Japanese chemical pharmaceutical Co., ltd; "ESN475V" (naphthalene type epoxy resin) and "ESN485" (naphthol novolac type epoxy resin) manufactured by Nissan chemical materials Co., ltd; "YL6121" (biphenyl type epoxy resin), "YX4000H", "YX4000HK" (bisxylenol type epoxy resin), "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi chemical corporation; "PG-100", "CG-500", manufactured by Osaka gas chemical company, "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenyl ethane type epoxy resin) manufactured by Mitsubishi chemical company; "WHR-991S" (phenol benzopyrrolone type epoxy resin) manufactured by Japanese chemical Co., ltd. These may be used alone or in combination of 1 or more than 2.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (B), the ratio of the amounts thereof (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.3 to 1:10, particularly preferably 1:0.5 to 1:5, in terms of mass ratio. By making the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range, the desired effect of the present invention can be remarkably obtained.

(B) The epoxy equivalent of the component is preferably 50g/eq to 5000g/eq, more preferably 50g/eq to 3000g/eq, still more preferably 80g/eq to 2000g/eq, still more preferably 110g/eq to 1000g/eq. Within this range, a cured product having sufficient crosslink density of the cured product of the resin composition layer can be obtained. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured according to JIS K7236.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of the component (B) is preferably 100 to 5000, more preferably 150 to 3000, and even more preferably 200 to 1500. The weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a Gel Permeation Chromatography (GPC) method.

From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the component (B) is preferably 3 mass% or more, more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition layer. The upper limit of the content of the epoxy resin is preferably 35 mass% or less, more preferably 30 mass% or less, and particularly preferably 25 mass% or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

(C) Curing agent

The resin composition layer may contain a curing agent (C) in combination with the component (A). The component (C) does not include a substance belonging to the component (B). As the curing agent (C), a compound having a function of curing the resin composition layer by reacting with the component (B) may be used, and examples thereof include: carbodiimide-based curing agents, active ester-based curing agents, phenol-based curing agents (phenol-based curing agents), naphthol-based curing agents, benzoxazine-based curing agents, cyanate-based curing agents, and the like. Among them, from the viewpoint of improving insulation reliability, the (C) curing agent preferably contains any one or more of a phenol curing agent, a naphthol curing agent, an active ester curing agent, and a cyanate curing agent. (C) The curing agent may be used alone or in combination of 2 or more.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a phenol structure or a naphthol-based curing agent having a phenol structure is preferable from the viewpoints of heat resistance and water resistance. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example: "MEH-7700", "MEH-7810", "MEH-7851" made by Ming He Chemicals, japan chemical company, "NHN", "CBN", "GPH", and "SN170", "SN180", "SN190", "SN475", "SN485", "SN 495V", "SN375", "SN395" made by Nissan Chemie, DIC "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA3018-50P", "EXB-9500", "KA-1163" made by Nissan chemical company.

Specific examples of the benzoxazine-based curing agent include: "HFB2006M" manufactured by Showa Polymer Co., ltd., and "P-d" and "F-a" manufactured by Sichuangji chemical industry Co., ltd.

Examples of the cyanate-based curing agent include: bisphenol A dicyanate, polyphenol cyanate, oligomeric (3-methylene-1, 5-phenylene cyanate), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2-bis (4-cyanooxy) phenylpropane, 1-bis (4-cyanooxyphenyl methane), bis (4-cyanooxy-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanooxyphenyl-1- (methylethylidene)) benzene, bis (4-cyanooxyphenyl) sulfide, bis (4-cyanooxyphenyl) ether, and polyfunctional cyanate resins derived from phenol novolac resins, cresol novolac resins, and the like, prepolymers obtained by triazinizing a part of these cyanate resins, and the like. Specific examples of the cyanate ester-based curing agent include: "PT30" and "PT60" manufactured by Lonza Japan company (phenol novolac type multifunctional cyanate resin), "ULL-950S" (multifunctional cyanate resin), "BA230" and "BA230S75" (prepolymer obtained by forming a trimer by triazining a part or the whole of bisphenol A dicyanate) are used.

The carbodiimide curing agent is a compound having 1 or more carbodiimide groups (-n=c=n-) in 1 molecule, and preferably has 2 or more carbodiimide groups in 1 molecule.

Specific examples of the carbodiimide-based curing agent include, for example, commercially available carbodiimide-based curing agents: CARBODILITE V-03 (carbodiimide equivalent: 216), V-05 (carbodiimide equivalent: 262), V-07 (carbodiimide equivalent: 200) manufactured by Niqing textile chemical Co., ltd.; v-09 (carbodiimide equivalent: 200); stabaxol P (carbodiimide equivalent: 302) manufactured by Rhein-chemie Co.

The active ester-based curing agent is not particularly limited, and generally, compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, and the like, are preferably used. The active ester curing agent is preferably obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include: benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or the naphthol compound include: hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, alpha-naphthol, beta-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, dicyclopentadiene type diphenol compounds, novolac (Phenolic Novolac) and the like. The "dicyclopentadiene type phenol compound" herein means a phenol compound obtained by condensing 2 molecules of phenol with 1 molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetyl compound of a novolac type resin, and an active ester compound containing a benzoyl compound of a novolac type resin are preferable, and among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. "dicyclopentadiene type diphenol structure" means a 2-valent structural unit composed of phenylene-dicyclopentene-phenylene.

As the commercial product of the active ester-based curing agent, examples of the active ester compound containing a dicyclopentadiene-type diphenol structure include "EXB-9451", "EXB-9460S", "HPC-8000-65T", "HPC-8000H-65TM", "HPC-8000L-65TM" (manufactured by DIC Co.); examples of the active ester compound having a naphthalene structure include "EXB-9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "HPC-8150-60T", "HPC-8150-62T", "HP-B-8151-62T" (manufactured by DIC Co.); examples of the active ester compound including an acetylation compound of a novolac resin include "DC808" (manufactured by mitsubishi chemical company); examples of the active ester compound including a benzoyl compound of a novolac resin include "YLH1026" (manufactured by Mitsubishi chemical corporation); examples of the active ester-based curing agent which is an acetylation product of a novolac resin include "DC808" (manufactured by mitsubishi chemical company); examples of the active ester-based curing agent which is a benzoyl compound of the novolac resin include "YLH1026" (manufactured by Mitsubishi chemical corporation), "YLH1030" (manufactured by Mitsubishi chemical corporation), "YLH1048" (manufactured by Mitsubishi chemical corporation), and examples of the active ester compound containing a styrene group include "PC1300-02-65MA" (manufactured by AIR WATER corporation).

(B) The ratio of the epoxy resin to the component (C) is represented by [ (total number of epoxy groups of the B) epoxy resin ]: the ratio of [ (total number of active groups of component (C) ] is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.3 to 1:3, still more preferably 1:0.5 to 1:2. Here, the "epoxy resin number" refers to a value obtained by adding all the values obtained by dividing the mass of the nonvolatile components of the epoxy resin present in the resin composition layer by the epoxy equivalent weight. The "active number of the component (C)" means a value obtained by adding all the values obtained by dividing the mass of the nonvolatile component (C) existing in the resin composition layer by the active group equivalent. The effect of the present invention can be remarkably obtained by setting the amount ratio of the component (C) to the epoxy resin within the above range.

The content of the component (C) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition layer, from the viewpoint of significantly obtaining the desired effect of the present invention. The upper limit is preferably 25 mass% or less, more preferably 20 mass% or less, and still more preferably 15 mass% or less.

(D) Radical polymerizable resin

The resin composition layer may contain a radical polymerizable resin (D) in combination with the component (a). The radical polymerizable resin (D) as the component (D) does not include any of the components (B) to (C).

The radical polymerizable resin is not particularly limited as long as it has 1 or more (preferably 2 or more) radical polymerizable unsaturated groups in 1 molecule. Examples of the radical polymerizable resin include resins having 1 or more groups selected from maleimide groups, vinyl groups, allyl groups, styryl groups, vinylphenyl groups, acryl groups, methacryl groups, fumaryl groups, and maleic groups as radical polymerizable unsaturated groups. Among them, from the viewpoint of remarkably obtaining the effect of the present invention, the radical polymerizable resin is preferably 1 or more selected from the group consisting of maleimide resins, (meth) acrylic resins and styrene resins, more preferably maleimide resins.

The maleimide resin is not particularly limited in kind as long as it has 1 or more (preferably 2 or more) maleimide groups (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl) in 1 molecule. Examples of the maleimide resin include: (1) Maleimide resins comprising an aliphatic skeleton (preferably an aliphatic skeleton having 36 carbon atoms derived from a dimer diamine) such as "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700" and "BMI-689" (all made by design molecule (Designer Molecules)) and "SLK6895-T90" (made by Xinyue chemical industry Co.); (2) Maleimide resins containing an indane skeleton described in Japanese patent application laid-open technical bulletin No. 2020-500211; (3) "MIR-3000-70MT" (manufactured by Japanese chemical Co., ltd.), "BMI-4000" (manufactured by Dai chemical Co., ltd.), "BMI-80" (manufactured by KI chemical Co., ltd.) and the like.

The type of the (meth) acrylic resin is not particularly limited as long as it has 1 or more (preferably 2 or more) (meth) acryl groups in 1 molecule, and may be a monomer or an oligomer. Here, the term "(meth) acryl" refers to the generic term of acryl and methacryl. Examples of THE methacrylic resin include (meth) acrylic resins such as "A-DOG" (manufactured by Nippon chemical industry Co., ltd.), "DCP-A" (manufactured by Kyowa chemical Co., ltd.), "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA" (manufactured by Japanese chemical Co., ltd.).

The styrene resin is not particularly limited as long as it has 1 or more (preferably 2 or more) styryl groups or vinylphenyl groups in 1 molecule, and may be a monomer or an oligomer. Examples of the styrene resin include styrene resins such as "OPE-2St", "OPE-2St 1200" and "OPE-2St 2200" (all manufactured by Mitsubishi gas chemical corporation), in addition to styrene monomers.

From the viewpoint of remarkably obtaining the effect of the present invention, the content of the component (D) is preferably 1 mass% or more, more preferably 3 mass% or more, still more preferably 5 mass% or more, preferably 15 mass% or less, still more preferably 13 mass% or less, and still more preferably 10 mass% or less, when the nonvolatile component in the resin composition layer is 100 mass%.

(E) Curing accelerator

The resin composition layer may contain a curing accelerator (E) in combination with the component (A). The curing accelerator (E) as the component (E) does not include any components belonging to the above-mentioned components (B) to (D). (E) The curing accelerator has a function as a curing catalyst for accelerating the curing of the (B) epoxy resin.

As the (E) curing accelerator, a compound that accelerates the curing of the epoxy resin may be used. Examples of such (E) curing accelerators include: phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, and the like. (E) The curing accelerator may be used alone or in combination of at least 2 kinds.

Examples of the phosphorus-based curing accelerator include: aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hexahydrophthalate hydrogen, tetrabutylphosphonium 2, 6-bis [ (2-hydroxy-5-methylphenyl) methyl ] -4-methylphenoxy, and di-t-butyldimethylphosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenyl phosphonium bromide, ethyltriphenyl phosphonium bromide, propyltriphenyl phosphonium bromide, butyltriphenyl phosphonium bromide, benzyltriphenyl phosphonium chloride, tetraphenyl phosphonium bromide, p-tolyltrimethyl phosphonium tetra-p-tolyl borate, tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium tetra-p-tolyl borate, triphenylethyl phosphonium tetraphenyl borate, tris (3-methylphenyl) ethyl phosphonium tetraphenyl borate, tris (2-methoxyphenyl) ethyl phosphonium tetraphenyl borate, (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyltriphenyl phosphonium thiocyanate, and the like; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-t-butylphosphine, trioctylphosphine, di-t-butyl (2-butenyl) phosphine, di-t-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexylphosphine; dibutyl phenyl phosphine, di-tert-butyl phenyl phosphine, methyl diphenyl phosphine, ethyl diphenyl phosphine, butyl diphenyl phosphine, diphenyl cyclohexyl phosphine, triphenyl phosphine, tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine, tri (4-ethylphenyl) phosphine, tri (4-propylphenyl) phosphine, tri (4-isopropylphenyl) phosphine, tri (4-butylphenyl) phosphine, tri (4-tert-butylphenyl) phosphine, tri (2, 4-dimethylphenyl) phosphine, tri (2, 5-dimethylphenyl) phosphine, tri (2, 6-dimethylphenyl) phosphine, tri (3, 5-dimethylphenyl) phosphine, tri (2, 4, 6-trimethylphenyl) phosphine, tri (2, 6-dimethyl-4-ethoxyphenyl) phosphine, tri (2-methoxyphenyl) phosphine, tri (4-ethoxyphenyl) phosphine, tri (4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridylphosphine, 1, 2-bis (diphenyl) phosphino-ethane, 1, 3-bis (diphenyl) phosphine, 2 '-diphenyl) phosphine, bis (2, 2' -diphenyl) phosphine, bis (2, 2-diphenyl) phosphine, etc.

Examples of urea-based curing accelerators include: 1, 1-dimethylurea; aliphatic dimethylureas such as 1, 3-trimethylurea, 3-ethyl-1, 1-dimethylurea, 3-cyclohexyl-1, 1-dimethylurea, and 3-cyclooctyl-1, 1-dimethylurea; 3-phenyl-1, 1-dimethylurea, 3- (4-chlorophenyl) -1, 1-dimethylurea, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea, 3- (2-methylphenyl) -1, 1-dimethylurea, 3- (4-methylphenyl) -1, 1-dimethylurea, 3- (3, 4-dimethylphenyl) -1, 1-dimethylurea, 3- (4-isopropylphenyl) -1, 1-dimethylurea, 3- (4-methoxyphenyl) -1, 1-dimethylurea, 3- (4-nitrophenyl) -1, 1-dimethylurea, 3- [4- (4-methoxyphenoxy) phenyl ] -1, 1-dimethylurea, 3- [4- (4-chlorophenoxy) phenyl ] -1, 1-dimethylurea, N- (1, 4-phenylene) bis (N ', N ' -dimethylurea, N- (4-dimethylphenyl) bis (N, N ' -dimethyltoluene) urea, etc.

Examples of the guanidine curing accelerator include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and the like.

Examples of the imidazole-based curing accelerator include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate adduct, and process for preparing the same, imidazole compounds such as 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins. Examples of commercial products of imidazole-based curing accelerators include: "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK-PW", "2PHZ-PW", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A" manufactured by the four-country chemical industry Co; "P200-H50" manufactured by Mitsubishi chemical corporation, etc.

Examples of the metal-based curing accelerator include: organometallic complexes or salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin, and the like. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate; organic copper complexes such as copper (II) acetylacetonate; organic zinc complexes such as zinc acetylacetonate (II); organic iron complexes such as iron (III) acetylacetonate; organonickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

Examples of the amine-based curing accelerator include: trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5, 4, 0) -undecene, and the like. As the amine-based curing accelerator, commercially available ones can be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine-Techno, inc.

From the viewpoint of remarkably obtaining the effect of the present invention, the content of the (E) curing accelerator is preferably 0.01 mass% or more, more preferably 0.03 mass% or more, still more preferably 0.05 mass% or more, preferably 1.5 mass% or less, still more preferably 1 mass% or less, and still more preferably 0.5 mass% or less, when the nonvolatile component in the resin composition layer is 100 mass%.

(F) Thermoplastic resin

The resin composition layer may contain a thermoplastic resin (F) in combination with the component (A). The thermoplastic resin (F) as the component (F) does not include any of the components (B) to (E).

Examples of the thermoplastic resin (F) include: phenoxy resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene oxide resin, polycarbonate resin, polyetheretherketone resin, polyester resin, and the like. (F) The thermoplastic resin may be used alone or in combination of 1 or more than 2.

Examples of the phenoxy resin include phenoxy resins having at least one skeleton selected from the group consisting of bisphenol a skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenol skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The end of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of the phenoxy resin include: "1256" and "4250" both made by Mitsubishi chemical corporation (phenoxy resins each having a bisphenol A skeleton); "YX8100" (phenoxy resin containing bisphenol S skeleton) manufactured by Mitsubishi chemical corporation; "YX6954" manufactured by Mitsubishi chemical corporation (phenoxy resin containing bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Kagaku Kogyo Co., ltd; "YL7500BH30", "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30" manufactured by Mitsubishi chemical corporation; etc.

Specific examples of the polyimide resin include "SLK-6100" manufactured by the more chemical industry Co., ltd., and "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by New Japan physical and chemical Co., ltd.

Examples of the polyvinyl acetal resin include: the polyvinyl formal resin and the polyvinyl butyral resin are preferably polyvinyl butyral resins. Specific examples of the polyvinyl acetal resin include: "Denka butyl 4000-2", "Denka butyl 5000-A", "Denka butyl 6000-C", "Denka butyl 6000-EP" manufactured by electric chemical industries, inc.; S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series, manufactured by the water chemical industry Co., ltd; etc.

Examples of the polyolefin resin include: ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

The polybutadiene resin includes, for example: a hydrogenated polybutadiene skeleton-containing resin, a hydroxyl-containing polybutadiene resin, a phenolic hydroxyl-containing polybutadiene resin, a carboxyl-containing polybutadiene resin, an acid anhydride group-containing polybutadiene resin, an epoxy group-containing polybutadiene resin, an isocyanate group-containing polybutadiene resin, a urethane group-containing polybutadiene resin, a polyphenylene ether-polybutadiene resin, and the like.

Specific examples of the polyamide-imide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by eastern spinning corporation. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane skeleton) manufactured by hitachi chemical company.

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by sumitomo chemical company.

Specific examples of the polysulfone resin include polysulfones "P1700" and "P3500" manufactured by the company sorvi high-performance polymer (Solvay Advanced Polymers).

Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "Ultem" manufactured by GE corporation.

Specific examples of the polycarbonate resin include: a hydroxyl group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxyl group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an isocyanate group-containing carbonate resin, a urethane group-containing carbonate resin, and the like. Specific examples of the polycarbonate resin include: "FPC0220" manufactured by Mitsubishi gas chemical corporation, "T6002" and "T6001" manufactured by Asahi chemical corporation (polycarbonate diol), and "C-1090" manufactured by Coleus corporation (C-2090) and "C-3090" (polycarbonate diol) are examples. Specific examples of the polyether-ether-ketone resin include "Sumiploy K" manufactured by sumitomo chemical company.

Examples of the polyester resin include: polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polypropylene terephthalate resin, polypropylene naphthalate resin, and polycyclohexane dimethyl terephthalate resin.

(F) The weight average molecular weight (Mw) of the thermoplastic resin is preferably more than 5,000, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less.

From the viewpoint of remarkably obtaining the effect of the present invention, the content of the thermoplastic resin (F) is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, particularly preferably 0.5 mass% or more, preferably 5 mass% or less, more preferably 3 mass% or less, particularly preferably 1.5 mass% or less, when the nonvolatile component in the resin composition layer is 100 mass%.

(G) Other additives

The resin composition layer may further contain (G) other additives as optional nonvolatile components in combination with the component (a). Examples of the other additives (G) include: an organic filler material; a polymerization initiator; organocopper compounds, organozinc compounds, organocobalt compounds, and other organometallic compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine, etc.; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; benton, montmorillonite and other thickening agents; an antifoaming agent such as an organosilicon antifoaming agent, an acrylic antifoaming agent, a fluorine antifoaming agent, and a vinyl resin antifoaming agent; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; an adhesion improver such as urea silane; adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; antioxidants such as hindered phenol antioxidants; fluorescent whitening agents such as stilbene derivatives; a surfactant such as a fluorine-based surfactant and an organosilicon-based surfactant; flame retardants such as phosphorus flame retardants (for example, phosphate compounds, phosphazene compounds, phosphinic acid compounds, and red phosphorus), nitrogen flame retardants (for example, melamine sulfate), halogen flame retardants, and inorganic flame retardants (for example, antimony trioxide); a dispersant such as a phosphate dispersant, a polyoxyalkylene dispersant, an acetylene dispersant, a silicone dispersant, an anionic dispersant, and a cationic dispersant; boric acid ester stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, carboxylic anhydride stabilizers, and the like; photopolymerization initiation aids such as tertiary amines; pyrazolines, anthracines, coumarins, xanthones, thioxanthones and other photosensitizers. (G) The other additives may be used alone or in combination of 1 or more than 2.

The resin composition layer may contain a solvent as a volatile component. From the viewpoint of adjusting the melt viscosity of the resin composition layer at 90 ℃, it is preferable that the amount of the solvent such as the organic solvent in the resin composition layer is small. The amount of the solvent (amount of residual solvent) in the resin composition layer is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, still further preferably 1.5% by mass or less, and particularly preferably 1% by mass or less. The lower limit is not particularly limited, but may be 0.0001 mass% or more, and the like.

Examples of the solvent include: aromatic hydrocarbons such as Methyl Ethyl Ketone (MEK), cyclohexanone, etc., aromatic hydrocarbons such as xylene and tetramethyl benzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc., esters such as ethyl acetate, butyl cellosolve acetate, carbitol acetate, diethylene glycol monoethyl ether acetate (ethyl diglycol acetate), aliphatic hydrocarbons such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha, etc. They may be used alone or in combination of 1 or more than 2.

The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 55 μm or less, from the viewpoints of thinning of the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition layer is a film. The lower limit of the thickness of the resin composition layer is not particularly limited, and is usually 5 μm or more and 10 μm or more.

< protective film >)

The resin sheet with a metal foil may further include a protective film as needed. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, the adhesion of refuse or the like to the surface of the resin composition layer or the occurrence of damage can be suppressed.

Examples of the protective film include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable. The surface of the protective film to be bonded to the resin composition layer may be subjected to a matting treatment, a corona treatment, or an antistatic treatment.

< method for producing resin sheet with Metal foil >

In the method for producing a metal foil-equipped resin sheet, for example, a resin varnish is prepared in which components contained in a resin composition layer are dissolved in a solvent, and the resin varnish is applied to a protective film by using a die coater or the like, and then dried to form a resin composition layer on the protective film. Then, a metal foil is bonded to the surface of the resin composition layer by using a roll laminator or the like, whereby a resin sheet with a metal foil can be produced. As the solvent, the above-mentioned solvents can be used.

Drying can be performed by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, and the resin composition layer is dried so that the content of the organic solvent is 10 mass% or less, preferably 5 mass% or less. When a resin varnish containing 30 to 60 mass% of a solvent is used, for example, depending on the boiling point of the solvent in the resin varnish, the resin composition layer can be formed by drying at 50 to 150℃for 3 to 10 minutes.

The resin sheet with the metal foil may be wound into a roll for storage. In the case where the resin sheet with a metal foil has a protective film, the protective film can be peeled off for use.

< physical Properties of resin sheet with Metal foil, etc.)

The resin sheet with metal foil obtained by heating the resin sheet with metal foil at 100℃for 30 minutes and then at 190℃for 120 minutes using a vacuum hot press to cure the resin composition layer showed no abnormal characteristics such as expansion between the metal foil and the cured product. That is, an insulating layer in which expansion generated between the conductor layer and the insulating layer is suppressed is provided. Even if the resin sheet with the metal foil was heated at 100 ℃ for 30 minutes and then at 190 ℃ for 120 minutes, no abnormality such as swelling was found on the small pieces of the insulating layer. The expansion evaluation can be performed by the method described in examples described later.

In the resin sheet with a metal foil of the present invention, the inorganic filler is contained in the resin composition layer in an amount of 40 mass% or more and 80 mass% or less based on 100 mass% of the nonvolatile component of the resin composition layer, and therefore exhibits a characteristic that the coefficient of linear thermal expansion (CTE) of the cured product of the resin composition layer is low. Therefore, the cured product brings about an insulating layer having a low linear thermal expansion coefficient. The linear thermal expansion coefficient is preferably 40 ppm/DEG C or less, more preferably 35 ppm/DEG C or less, and still more preferably 30 ppm/DEG C or less. The lower limit is not particularly limited, and may be 1 ppm/DEG C or more. The linear thermal expansion coefficient can be measured by the method described in examples described below.

In the resin sheet with a metal foil of the present invention, the inorganic filler is contained in the resin composition layer in an amount of 40 mass% or more and 80 mass% or less based on 100 mass% of the nonvolatile component of the resin composition layer, and therefore, the resin composition layer cured by a vacuum hot press generally has a high glass transition temperature (Tg) characteristic. Thus, an insulating layer having a high glass transition temperature is provided. The glass transition temperature of the cured product of the resin composition layer is preferably 140℃or higher, more preferably 145℃or higher, and still more preferably 150℃or higher. The upper limit is not particularly limited, and may be, for example, 300℃or lower. The glass transition temperature (Tg) can be measured by the method described in examples described below.

In the metal foil-equipped resin sheet of the present invention, since the first surface of the metal foil has a maximum height roughness (Rz) of 1000nm or more, the first surface is continuously formed with projections. In the resin sheet with a metal foil of the present invention, since the metal foil and the resin composition layer are bonded so that the peel strength between the metal foil and the resin composition layer is 0.01kgf/cm or more and 0.3kgf/cm or less, a part of the protrusions continuously provided on the first surface is buried in the resin composition layer. Therefore, the metal foil and the resin composition layer have voids formed continuously between the protrusions at the interface therebetween. When the resin sheet with metal foil is immersed in water, the water is immersed in the voids of the resin sheet with metal foil. At the site of the void where water is immersed, color changes. Therefore, when the discolored part is spread over the whole of the resin sheet with the metal foil, it can be evaluated that the void is continuous. When the resin sheet with a metal foil of the present invention is immersed in water, the resin sheet with a metal foil is discolored as a whole. Therefore, the resin sheet with a metal foil of the present invention is continuously formed with voids. The continuity of the voids was evaluated by the method described in examples described below.

By using the resin sheet with a metal foil of the present invention, an insulating layer with suppressed generation of expansion and low linear thermal expansion coefficient can be provided. Therefore, the resin sheet with a metal foil of the present invention can be suitably used as a resin sheet for forming two layers of an insulating layer and a conductor layer (for forming an insulating layer and a conductor layer) in the production of a circuit board, as a resin sheet for forming two layers of an insulating layer and a conductor layer (for forming an insulating layer and a conductor layer using a vacuum thermocompression process) in the production of a circuit board, as a resin sheet for forming two layers of an insulating layer and a conductor layer (for forming an insulating layer and a conductor layer) using a vacuum thermocompression process, and as a resin sheet for forming two layers of an insulating layer and a conductor layer using a vacuum thermocompression process in the production of a printed wiring board.

[ Circuit Board ]

The circuit board of the present invention can be manufactured using the resin sheet with a metal foil of the present invention. That is, a circuit board including an insulating layer formed of a cured product of the resin composition layer of the resin sheet with a metal foil of the present invention and a conductor layer formed of a metal foil can be provided.

As one embodiment of the circuit board, there is a printed wiring board. The printed wiring board includes an insulating layer formed of a cured product of the resin composition layer of the resin sheet with a metal foil of the present invention, and a conductor layer formed of a metal foil.

The printed wiring board can be produced, for example, by a method comprising the steps of (I) and (II) below using the resin sheet with a metal foil described above:

(I) And (II) a step of laminating a resin composition layer in the metal foil-equipped resin sheet on the inner substrate by vacuum hot press treatment, and a step of thermally curing the resin composition layer to form an insulating layer.

The "inner substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include: glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene oxide substrates, and the like. The substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be subjected to patterning. An inner layer substrate having a conductor layer (circuit) formed on one or both surfaces of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, in manufacturing a printed wiring board, an intermediate product to be further formed with an insulating layer and/or a conductor layer is also included in the "inner layer substrate" described in the present invention. In the case where the printed wiring board is a component-embedded circuit board, an inner layer substrate having a component embedded therein may be used.

In the lamination of the inner layer substrate and the resin sheet with metal foil, the resin composition layer of the resin sheet with metal foil is laminated by vacuum hot press treatment so as to be bonded to the inner layer substrate.

First, the inner substrate and the resin sheet with metal foil are mounted on a vacuum hot press apparatus so that the resin composition layer of the resin sheet with metal foil is bonded to the inner substrate. Then, a vacuum thermocompression bonding process is performed under reduced pressure to thermocompression bond the inner substrate and the resin composition layer.

The inner substrate and the resin sheet with metal foil may be attached to a vacuum hot press apparatus via a metal plate such as a buffer paper or a stainless steel plate (SUS plate), a release film, or the like.

The vacuum hot press treatment may be performed using a conventionally known vacuum hot press apparatus in which a metal plate such as a heated SUS plate is used to press the inner substrate and the resin sheet with the metal foil from both sides thereof. Examples of commercially available vacuum hot press apparatuses include "VH1-1603" manufactured by north Sichuan refiner.

The vacuum hot pressing treatment may be performed only 1 time, or may be repeated 2 or more times. When the pressure is applied repeatedly 2 times or more, the pressure, heating temperature, pressing time, etc. may be the same or different.

In the vacuum hot press treatment, the pressure of the press (pressing force) is preferably 5kgf/cm ² The above is more preferably 10kgf/cm ² The above is more preferably 15kgf/cm ² Above, preferably 50kgf/cm ² Hereinafter, it is more preferably 35kgf/cm ² Hereinafter, it is more preferably 25kgf/cm ² The following is given.

In the vacuum hot press treatment, the pressure of the atmosphere, that is, the pressure (degree of depressurization) (vacuum degree) at the time of depressurization in the chamber of the laminated structure storing the treatment object is preferably 3×10 ^-2 MPa or less, more preferably 1X 10 ^-2 And MPa or below. The lower limit is not particularly limited and may be 1X 10 ^-10 MPa or more, etc.

In the vacuum hot press treatment, the heating temperature varies depending on the composition of the resin composition layer, and is preferably 80 ℃ or higher, more preferably 90 ℃ or higher, and still more preferably 100 ℃ or higher. The upper limit of the heating temperature is not particularly limited, and may be generally 300℃or lower. The insulating layer may be formed by thermally curing the resin composition layer by heating in the vacuum hot press treatment.

In the vacuum hot press treatment, the pressing time is preferably 5 minutes or more, more preferably 10 minutes or more, and still more preferably 15 minutes or more. The upper limit is not particularly limited, but is preferably 300 minutes or less, more preferably 200 minutes or less, and still more preferably 150 minutes or less.

In the lamination step using the vacuum hot press treatment, when the pressure in the chamber has been reduced, air is discharged from the space between the metal foil and the resin composition layer through the space. Then, after the air is discharged from the void, the inner layer substrate is bonded to the resin composition layer by pressing, and the resin composition layer is bonded to the metal foil. As described above, since the pressing is performed after the air is discharged from the void, the expansion can be suppressed.

After laminating a resin sheet with a metal foil on the inner layer substrate by vacuum pressing treatment, the resin composition layer is thermally cured to form an insulating layer in step (II). As a method for thermally curing the resin composition layer, for example, when a pressing treatment is performed by a vacuum hot press treatment, the resin composition layer is thermally cured by heat at the time of pressing to form an insulating layer.

The heat curing condition of the resin composition layer is not particularly limited, and conditions generally employed in forming an insulating layer of a printed wiring board can be used.

For example, the heat curing condition of the resin composition layer varies depending on the kind of the resin composition layer, etc., and the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, still more preferably 170 to 210 ℃. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.

The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer may be preheated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes) at a temperature of 50 ℃ or more and less than 120 ℃ (preferably 60 ℃ or more and 115 ℃ or less, more preferably 70 ℃ or more and 110 ℃ or less) before the resin composition layer is thermally cured.

Since the resin sheet with a metal foil used in the present invention contains a metal foil, the step (III) may include a step of forming a conductor layer (circuit) by a subtractive method or a modified semi-additive method.

In the step (III), the conductor layer may be formed by a subtractive method or a modified semi-additive method using the metal foil in the resin sheet with the metal foil.

In the subtractive method, unnecessary portions (non-circuit forming portions) of the metal foil are selectively removed by etching or the like to form a circuit. The formation of the circuit based on the subtractive method may be performed according to a known procedure. For example, subtractive process-based circuit formation may be implemented by a method comprising: i) A resist is provided on the surface of the metal foil (i.e., the surface opposite to the "surface bonded to the resin composition layer"), the resist is ii) exposed and developed to form a wiring pattern, iii) the exposed metal foil portion is etched and removed, and iv) the resist is removed.

In the improved semi-additive method, a non-circuit-forming portion of a metal foil is protected by plating resist, a metal such as copper is thickened on the circuit-forming portion by electrolytic plating, the plating resist is removed, and the metal foil other than the circuit-forming portion is removed by etching to form a circuit. The circuit formation by the modified semi-additive method can be performed according to a known procedure. For example, the improved semi-additive based circuit formation may be implemented by a method comprising: i) The method comprises providing an anti-plating layer on the surface of a metal foil (i.e., the surface opposite to the "surface bonded to the resin composition layer"), ii) exposing and developing the anti-plating layer to form a wiring pattern, iii) electrolytic plating via the anti-plating layer, iv) removing the anti-plating layer, and v) etching and removing the metal foil except for the circuit forming portion. In the case where the metal foil is thick, before i), the entire surface of the metal foil may be thinned by etching or the like so that the metal foil has a desired thickness (usually 5 μm or less, 4 μm or less, or 3 μm or less).

In the case of manufacturing a printed wiring board, the step (IV) of forming the hole and the step (V) of roughening the insulating layer may be further performed. These steps (IV) to (V) may be performed according to various methods known to those skilled in the art for use in manufacturing a printed wiring board. If necessary, the insulating layer and the conductor layer may be formed repeatedly in the steps (I) to (V) to form a multilayer wiring board.

[ semiconductor device ]

The semiconductor device of the present invention includes the circuit board or the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the circuit board or the printed wiring board of the present invention.

Examples of the semiconductor device include various semiconductor devices used for electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric trains, ships, aircraft, and the like).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conductive portion" refers to a "portion of the printed wiring board that transmits an electrical signal", and may be a surface or a buried portion. The semiconductor chip is not particularly limited as long as it is a circuit element made of a semiconductor.

The method for mounting the semiconductor chip in the production of the semiconductor device is not particularly limited as long as the semiconductor chip can effectively function, and specifically, there is mentioned: a wire bonding mounting method, a flip chip mounting method, a mounting method based on a build-up non-rugged layer (BBUL), a mounting method based on an Anisotropic Conductive Film (ACF), a mounting method based on a non-conductive film (NCF), and the like. Here, "mounting method based on a build-in non-rugged layer (BBUL)" means: "mounting method for directly embedding a semiconductor chip in a recess of a printed wiring board and connecting the semiconductor chip to a wiring on the printed wiring board".

Examples

The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. Hereinafter, "part" and "%" refer to "part by mass" and "% by mass", respectively, unless otherwise indicated.

< blending example 1> production of resin varnish 1

To 20 parts of bisphenol A type epoxy resin (Mitsubishi chemical corporation "828EL", about 180g/eq in epoxy equivalent) and 20 parts of biphenyl type epoxy resin (Japan chemical corporation "NC3000L", about 269g/eq in epoxy equivalent) were added 40 parts of Methyl Ethyl Ketone (MEK) and the mixture was heated and dissolved with stirring. It was cooled to room temperature to prepare an epoxy resin-dissolved composition. To this epoxy resin-dissolved composition were mixed 10 parts of a triazine skeleton-containing phenol-based curing agent ("LA-3018-50P" manufactured by DIC corporation, a 2-methoxypropanol solution having an active group equivalent of about 151g/eq., a nonvolatile content of 50%), 5 parts of an active ester compound (HPC-8000-65T "manufactured by DIC corporation, a toluene solution having an active ester group equivalent of about 223g/eq., a nonvolatile content of 65%), 180 parts of spherical silica surface-treated with a silane coupling agent (KBM-573" manufactured by siem corporation), 4 parts of an amine-based curing accelerator (4-Dimethylaminopyridine (DMAP), a MEK solution having a solid content of 5 mass%, a MEK solution having a solid content of 10 mass%, and 5 parts of an imidazole-based curing accelerator (manufactured by quadtime corporation), and uniformly dispersed by a high-speed rotary mixer to prepare a varnish 1.

< blending example 2> production of resin varnish 2

To 10 parts of bisphenol A type epoxy resin (product of Mitsubishi chemical corporation, "828EL", about 180 g/eq) in terms of epoxy equivalent, 20 parts of biphenyl type epoxy resin (product of Japan chemical corporation "NC3000L", about 269 g/eq) in terms of epoxy equivalent, 10 parts of naphthylene ether type epoxy resin (product of DIC corporation "HP-6000", about 250 g/eq) in terms of epoxy equivalent were added 20 parts of Methyl Ethyl Ketone (MEK) and the mixture was heated and dissolved with stirring. It was cooled to room temperature to prepare an epoxy resin-dissolved composition. To this epoxy resin-dissolved composition, 15 parts of a triazine skeleton-containing phenol-based curing agent (MEK solution having an active group equivalent of about 125g/eq. And a nonvolatile content of 60%) 15 parts of a naphthol-based curing agent (SN-485; made by Nitro chemical materials Co., ltd., "SN-485; having a hydroxyl equivalent of about 205 g/eq.) 10 parts of a phenoxy resin (YX 7553BH 30; made by Mitsubishi chemical Co., ltd.," KBM-573; having a nonvolatile content of 30% by mass) 1:1 with cyclohexanone) 8 parts of spherical silica surface-treated with a silane coupling agent (SO-C2; made by Yakuma Co., ltd., "KBM-573; having an average particle diameter of 0.5 μm) 100 parts, and 5 parts of an imidazole-based curing accelerator (MEK solution having a solid content of 10% by mass) were uniformly dispersed by a high-speed rotary mixer, to prepare a resin varnish 2.

< blending example 3> production of resin varnish 3

To 15 parts of bisphenol A type epoxy resin (product of Mitsubishi chemical corporation, "828EL", about 180g/eq in epoxy equivalent), 10 parts of naphthalene type epoxy resin (product of Suzuki chemical corporation, "ESN475V", about 332g/eq in epoxy equivalent) and 10 parts of naphthylene ether type epoxy resin (product of DIC, "HP-6000", about 250g/eq in epoxy equivalent) were added 40 parts of Methyl Ethyl Ketone (MEK) and the mixture was heated and dissolved with stirring. It was cooled to room temperature to prepare an epoxy resin-dissolved composition. To this dissolved composition, 30 parts of an active ester compound (HPC-8000-65T, available from DIC Co., ltd., active ester equivalent weight of about 223g/eq., non-volatile fraction of 65% in toluene solution), 20 parts of a bisphenol A dicyanate prepolymer (BA 230S75, available from Lonza Japan Co., ltd., cyanate equivalent weight of about 232g/eq., non-volatile fraction of 75% by mass in MEK solution), 8 parts of a phenoxy resin (YX 7553BH30, available from Mitsubishi chemical Co., ltd., 1:1 solution of 30% by mass in MEK and cyclohexanone), 180 parts of spherical silica (SO-C2, available from Szechwan chemical Co., ltd., average particle size of 0.5 μm), 4 parts of an amine curing accelerator (4-Dimethylaminopyridine (DMAP), 5% by mass in MEK solution, available from solid content of 5% in MEK), 1 part of cobalt (III) acetylacetonate (Tokyo Co., available from Tokyo chemical Co., ltd.), and 3 parts of a 1% by mass in MEK were mixed, and a varnish was uniformly mixed, and a varnish was prepared.

< blending example 4> production of resin varnish 4

In the case of the blending example 1,

1) The amount of biphenyl type epoxy resin (NC 3000L, about 269g/eq of epoxy equivalent, manufactured by Japanese chemical Co., ltd.) was changed from 20 parts to 5 parts,

2) Further, 10 parts of a bisxylenol type epoxy resin (YX 4000HK manufactured by Mitsubishi chemical corporation) was used,

3) Further, 5 parts of an alicyclic epoxy resin (CELLOXIDE 2021P, manufactured by Kagaku Co., ltd., epoxy equivalent weight: about 137 g/eq.) was used,

4) The amount of the triazine skeleton-containing phenol curing agent (LA-3018-50P, manufactured by DIC Co., ltd., "2-methoxypropanol solution having an active group equivalent of about 151g/eq., and a nonvolatile content of 50%) was changed from 10 parts to 5 parts,

5) The amount of the active ester compound (toluene solution having an active ester group equivalent of about 223g/eq. And a nonvolatile content of 65%) was changed from 50 parts to 30 parts by weight,

6) 180 parts of spherical silica (SO-C2, average particle diameter 0.5 μm, manufactured by Yakuma Co., ltd.) surface-treated with a silane coupling agent (KBM-573, manufactured by Xinshi chemical industries Co., ltd.) was changed to 100 parts of spherical silica (UFP-30, average particle diameter 0.3 μm, manufactured by Denka Co., ltd.) surface-treated with a silane coupling agent (KBM-573, manufactured by Xinshi chemical industries Co., ltd.),

7) Further, 15 parts of maleimide resin (MIR-3000-70 MT manufactured by Japanese chemical Co., ltd.) containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group was used,

8) Further, 5 parts of a styrene resin (manufactured by Mitsubishi gas chemical corporation, "OPE-2St 1200") was used;

except for the above, a resin varnish 4 was produced in the same manner as in blending example 1.

< blending example 5> production of resin varnish 5

In the case of the blending example 1,

1) The amount of spherical silica (SO-C2, manufactured by Yadu MAX) surface-treated with a silane coupling agent (KBM-573, manufactured by Xin Yue chemical industries Co., ltd.) was changed from 180 parts to 50 parts,

2) Further, 5 parts of a phenoxy resin (YX 7553BH30, 1:1 solution of MEK and cyclohexanone, 30% by mass of nonvolatile matter, manufactured by Mitsubishi chemical corporation) was used,

3) Further using 2 parts of rubber particles (Aica Industrial Co., ltd. "STAPHYLOID AC 3816N");

except for the above, a resin varnish 5 was produced in the same manner as in blending example 1.

< blending example 6> production of resin varnish 6

In the case of the blending example 1,

1) The amount of spherical silica (SO-C2, manufactured by Yakuma Co., ltd., average particle diameter of 0.5 μm) surface-treated with a silane coupling agent (KBM-573, manufactured by Xinyue chemical industries Co., ltd.) was changed from 180 parts to 330 parts,

2) Further, 8 parts of a phenoxy resin (YX 7553BH30, 1:1 solution of MEK and cyclohexanone, 30% by mass of nonvolatile matter, manufactured by Mitsubishi chemical corporation) was used;

except for the above, a resin varnish 6 was produced in the same manner as in blending example 1.

< measurement of glass transition temperature and coefficient of linear thermal expansion of cured product of resin composition layer >

A glass cloth-based epoxy resin double-sided copper-clad laminate (R5715 ES, manufactured by Song Co., ltd., thickness: 0.7mm,255mm square) was laminated on the release agent untreated surface of a PET film (manufactured by Lende Co., ltd. "501010", thickness: 50 μm, 240mm square), and four sides thereof were fixed with a polyimide tape (width: 10 mm) (hereinafter sometimes referred to as "fixed PET film").

Resin varnishes 1 to 6 prepared in blending examples 1 to 6 were applied to the release treated surface of the "fixed PET film" by a die coater so that the thickness of the dried resin composition layer became 40. Mu.m, and dried at 80℃to 120℃for 10 minutes (average 100 ℃) to obtain a resin sheet. Next, the resin composition layer was put into an oven at 190 ℃ and then thermally cured under curing conditions of 90 minutes. After heat curing, the polyimide tape was peeled off, and the cured product was removed from the glass cloth base epoxy resin double-sided copper-clad laminate, and further, a PET film (manufactured by linde corporation, "501010") was peeled off, to obtain a sheet-like cured product. The obtained cured product was referred to as "cured product for evaluation".

The cured product for evaluation was cut into test pieces having a width of about 5mm and a length of about 15mm, and subjected to thermomechanical analysis by a tensile load method using a thermomechanical analysis apparatus (Rigaku "Thermo Plus TMA 8310"). Specifically, after the test piece was mounted on the thermal mechanical analyzer, the test piece was continuously measured 2 times under a measurement condition of a load of 1g and a temperature rise rate of 5 ℃/min. Then, in the second measurement, a glass transition temperature (Tg;. Degree. C.) and an average linear thermal expansion coefficient (CTE; ppm/. Degree. C.) in a range from 25℃to 150℃were calculated, and the determination was made on the basis of the following determination criteria;

o: an average thermal expansion coefficient of 40 ppm/DEG C or less

X: the average coefficient of thermal expansion exceeds 40 ppm/. Degree.C.

< measurement of melt viscosity at 90 ℃ of resin composition layer >

The resin varnishes 1 to 6 obtained in blending examples 1 to 6 were applied to a release surface of a polyethylene terephthalate film (AL 5, thickness 38 μm, manufactured by Leideco Co., ltd.) with a release treatment as a protective film by a die coater so that the thickness of the resin composition layer became 40 μm, and dried at 80 to 120 ℃ (average 100 ℃) for 6 minutes. After the protective film was peeled off, 25 sheets of the same resin composition layers were stacked to obtain a resin composition layer laminate having a thickness of 1.25 mm. Next, the resin composition layer laminate was die-cut in the lamination direction with a diameter of 20mm, and a measurement sample was produced. The prepared measurement sample was subjected to measurement of dynamic viscoelasticity modulus using a dynamic viscoelasticity measuring apparatus (Rheogel-G3000, manufactured by UBM Co.) at a temperature rise rate of 5 ℃/min from 60℃to 200℃and a measurement temperature interval of 2.5℃at a vibration frequency of 1Hz and a strain of 5deg to obtain a melt viscosity curve, from which the melt viscosity (poise) at 90℃was determined, and the measurement was carried out on the basis of the following judgment standard;

O: melt viscosity at 90 ℃ is 5,000 poise or more and 100,000 poise or less

X: melt viscosity at 90 ℃ is less than 5,000 poise or more than 100,000 poise.

TABLE 1

(Table 1)

* In the table, the content of the component (a) represents the content of 100 mass% of the nonvolatile component in the resin composition layer.

< example 1> production of resin sheet with Metal foil 1

The resin varnish 1 was applied on the release surface of a polyethylene terephthalate film (AL 5, manufactured by linde co., ltd., thickness 38 μm) with a release treatment as a protective film by a die coater so that the thickness of the resin composition layer became 40 μm, and dried at 80 to 120 ℃ (average 100 ℃) for 6 minutes. Next, a carrier-equipped copper foil including a carrier copper foil and an extra Thin copper foil (Micro Thin MT18Ex manufactured by mitsunobu metal mining corporation), an extra Thin copper foil having a thickness of 3 μm/a carrier copper foil having a thickness of 18 μm, and a maximum height roughness (Rz) of 4900nm were laminated on the surface of the resin composition layer using a roll laminator (manufactured by mitsunobu metal mining corporation) under conditions of a roll pressing force of 0.25MPa, a transfer speed of 0.3m/min, and a roll temperature of 90 ℃.

< example 2> production of resin sheet with Metal foil 2

In the case of the embodiment of the present invention in which the sample is a solid,

1) Changing the resin varnish 1 into a resin varnish 2,

2) The copper foil with carrier (Micro Thin MT18Ex, manufactured by Mitsui Metal mining Co., ltd., "ultra Thin copper foil with thickness of 3 μm/carrier copper foil with thickness of 18 μm, maximum height roughness (Rz) 4900 nm) having a carrier copper foil and an ultra Thin copper foil was changed to copper foil (JDLC, manufactured by JX Metal mining Co., ltd.," copper foil with thickness of 12 μm, maximum height roughness (Rz) 8200 nm);

except for the above, a resin sheet 2 with a metal foil was obtained in the same manner as in example 1.

< example 3> production of resin sheet 3 with Metal foil

In example 1, the resin varnish 1 was changed to a resin varnish 3. Except for the above, a resin sheet 3 with a metal foil was obtained in the same manner as in example 1.

< example 4> production of resin sheet with Metal foil 4

In example 1, the resin varnish 1 was changed to a resin varnish 4. Except for the above, a resin sheet 4 with a metal foil was obtained in the same manner as in example 1.

Comparative example 1> production of resin sheet 5 with Metal foil

In example 2, the resin varnish 2 was changed to a resin varnish 5. Except for the above, a resin sheet 5 with a metal foil was obtained in the same manner as in example 2.

Comparative example 2 production of resin sheet with Metal foil 6

In example 1, a film with a metal film (film in which a cellulose layer having a thickness of 1 μm and a copper layer having a thickness of 0.5 μm were formed in this order on a polyethylene terephthalate film having a thickness of 38 μm, and a maximum height roughness (Rz) of 300 nm) was obtained by changing a copper foil with a carrier comprising a carrier copper foil and an extra Thin copper foil (Micro Thin MT18Ex, manufactured by Mitsui metal mining Co., ltd., "extra Thin copper foil having a thickness of 3 μm/carrier copper foil having a thickness of 18 μm, and maximum height roughness (Rz) of 4900 nm) to those described in Japanese patent No. 5633124. Except for the above, a resin sheet 6 with a metal foil was obtained in the same manner as in example 2.

Comparative example 3 production of resin sheet with Metal foil 7

In comparative example 2, the resin varnish 2 was changed to a resin varnish 6. Except for the above, the same procedure as in comparative example 2 was carried out, but since the melt viscosity of the resin varnish 6 was high, the resin varnish 6 could not be applied, and the film with the metal film could not be laminated with a roll laminator. That is, in comparative example 3, since the resin varnish 6 could not be applied on the protective film, the film with the metal film could not be bonded on the resin composition layer.

< maximum height roughness (Rz) measurement of Metal foil >

The Rz value was obtained from the film with a carrier copper foil (Micro Thin MT18Ex, manufactured by Mitsui metal mining Co., ltd., extra Thin copper foil with a thickness of 3 μm/carrier copper foil with a thickness of 18 μm), a copper foil (JDLC, manufactured by JX metal mining Co., ltd., copper foil with a thickness of 12 μm) and a film with a metal film (film obtained by sequentially forming a cellulose layer with a thickness of 1 μm and a copper layer with a thickness of 0.5 μm on a polyethylene terephthalate film with a thickness of 38 μm) described in Japanese patent No. 5633124, which were used in examples and comparative examples, using a noncontact surface roughness meter (WYKO NT3300, manufactured by Veeco Instruments Co., ltd.) by using a VSI mode and a 50-fold lens and setting the measurement range to 121 μm×92 μm. The average value of the measured 10 points at a distance of 3cm or more is obtained.

< measurement of peel Strength between Metal foil and resin composition layer, evaluation of expansion after lamination >

(1) Manufacture of base-treated inner substrate

A glass cloth-based epoxy resin double-sided copper-clad laminate having a copper foil on the surface (copper foil thickness: 18 μm, substrate thickness: 0.8mm, manufactured by Songshi Co., ltd. "R1515A") was prepared. The copper foil on the surface of the laminate was etched with a copper etching amount of 1 μm using a microetching agent (CZ 8101, MEC corporation), and roughened. Then, the substrate was dried at 190℃for 30 minutes to prepare a base-treated inner substrate.

(2) Determination of peel strength

The base-treated inner layer substrate was cut into pieces of 30mm by 120mm, and double-sided tape (Nicetack NW-25 manufactured by Nichiba Co., ltd.) was attached. After the release paper of the double-sided tape was peeled off, the protective film was peeled off from the metal foil-equipped resin sheet obtained in examples and comparative examples, and the resin composition layer was bonded to the double-sided tape in contact therewith.

Examples 1, 3 and 4 were obtained by peeling the carrier foil, comparative examples 2 and 3 were obtained by removing the polyethylene terephthalate film and the cellulose layer of the protective film, and example 2 and comparative example 1 were obtained by directly sealing the four-sided reverse embossed copper foil conductive tape (3M japanese company "3245") so that the plating solution does not enter.

Then, copper sulfate plating was performed until the total thickness of the metal foil became 20 μm, and drying was performed at 130℃for 30 minutes. Then, a cut mark having a width of 10mm and a length of 100mm was cut by a cutter, one end thereof was peeled off and held by a jig (AUTO COM type test machine "AC-50C-SL" manufactured by TSE Co.), and a load (kgf/cm) when peeled off at a speed of 50 mm/min in the vertical direction by 20mm was measured at room temperature according to JIS C6481, and was determined according to the following determination criteria. In comparative examples 1 and 2, the peel strength between the resin composition layer and the double-sided tape was 1.28kgf/cm, and therefore, it was estimated that the peel strength between the metal foil and the resin composition layer was higher than 1.28kgf/cm. In comparative example 3, since the resin varnish 6 could not be applied, the metal foil could not be bonded to the resin composition layer, and thus the peel strength could not be measured;

O: the peel strength is 0.01kgf/cm or more and less than 0.30kgf/cm

X: the peel strength was less than 0.01kgf/cm or more than 0.30kgf/cm, or a test piece could not be produced.

(2) Evaluation of expansion after lamination

Resin sheets with metal foil obtained in examples and comparative examples were laminated on both sides of the base treatment inner substrate using a vacuum hot press (VH 1-1603, manufactured by hokken refiner co.) so that the resin composition layer was in contact with the base treatment inner substrate. The pressing conditions were set to a reduced pressure (vacuum) of 1×10 ^-3 Under reduced pressure of MPa or less, the pressure condition is 20kgf/cm ² The heating conditions were carried out at a press-in temperature of 100℃for 30 minutes and a press-in temperature of 190℃for 120 minutes in stage 2, to obtain a substrate for evaluation. The evaluation substrate was cut into small pieces of 100mm×50mm, and the pieces were visually inspected and evaluated according to the following evaluation criteria. In comparative example 3, since the resin varnish 6 could not be applied, the metal foil could not be bonded to the resin composition layer, and thus the expansion after lamination could not be evaluated;

o: the tablet is completely free of anomalies

X: the tablet has swelling anomalies.

< evaluation of continuity of voids >

The resin sheets with metal foil obtained in examples and comparative examples were cut into 20mm×20mm, and after peeling off the protective film, they were put into a glass beaker containing 50mL of pure water. Next, the glass beaker containing the resin sheet with the metal foil was left in a desiccator, and was depressurized to 10kPa using a diaphragm vacuum pump, and kept for 10 minutes. Then slowly returned to atmospheric pressure for about 30 seconds. If the resin sheet with metal foil is immersed in water, the water is immersed in the voids of the resin sheet with metal foil, and the color of the portion of the voids in which the water is immersed is changed. When the discolored part was spread over the whole of the resin sheet with the metal foil, it was evaluated that the void was continuous. In comparative example 3, since the resin varnish 6 could not be applied, the metal foil could not be bonded to the resin composition layer, and thus the continuity of the void could not be evaluated;

o: the voids are continuous: water is immersed in the gaps

X: no voids, or discontinuous voids, and no water is immersed in the voids.

TABLE 2

(Table 2)

Symbol description

1. Resin sheet with metal foil

2. Metal foil

2a first side

21. Protrusions

22. Void space

3. Resin composition layer

4. And a protective film.

Claims

1. A resin sheet with a metal foil, the resin sheet with a metal foil comprising:

metal foil having a first face, and

a resin composition layer bonded to the first surface of the metal foil,

the resin composition layer contains (A) an inorganic filler,

the peel strength between the metal foil and the resin composition layer is 0.01kgf/cm or more and 0.3kgf/cm or less.

2. The resin sheet with a metal foil according to claim 1, wherein a void is continuously formed at an interface of the first face of the metal foil and the resin composition layer.

3. The resin sheet with metal foil according to claim 1, wherein the resin composition layer contains (B) an epoxy resin.

4. The resin sheet with metal foil according to claim 1, wherein the resin composition layer contains (C) a curing agent.

5. The resin sheet with a metal foil according to claim 1, wherein the cured product of the resin composition layer has a linear thermal expansion coefficient of 40ppm/°c or less.

6. The resin sheet with a metal foil according to claim 1, wherein a protective film is provided on a face of the resin composition layer which is not joined to the metal foil.

7. The resin sheet with a metal foil according to claim 6, wherein the protective film is subjected to a mold release treatment.

8. The resin sheet with metal foil according to claim 1, wherein the metal foil is a copper foil.

9. A circuit substrate, comprising:

an insulating layer formed of a cured product of the resin composition layer of the resin sheet with a metal foil according to any one of claims 1 to 8, and

a conductor layer formed using the metal foil of the resin sheet with metal foil according to any one of claims 1 to 8.

10. A semiconductor device comprising the circuit substrate of claim 9.