CN113442537A

CN113442537A - Resin sheet

Info

Publication number: CN113442537A
Application number: CN202110314051.1A
Authority: CN
Inventors: 渡边真俊
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2020-03-27
Filing date: 2021-03-24
Publication date: 2021-09-28
Also published as: TW202140642A; KR20210120885A; JP2021154641A; JP7459611B2

Abstract

The invention provides a resin sheet and the like capable of obtaining a cured product with low dielectric loss tangent and excellent insulation reliability. The resin sheet comprises a support and a resin composition layer containing a resin composition provided on the support, wherein the oxygen permeability of the support measured by a method according to JIS K7126 is 20cc/m in an atmosphere of 23 ℃ and 50% RH²As for seeds or seeds, the amount of solvent contained in the resin composition layer is 5% by mass or less, and the resin composition contains any of (A-1) a volatile epoxy resin and (B) a radical polymerizable resin.

Description

Resin sheet

Technical Field

The present invention relates to a resin sheet. Further, the present invention relates to a printed wiring board and a semiconductor device formed using the resin sheet, and a method for manufacturing a printed wiring board.

Background

As a manufacturing technique of a printed wiring board, a manufacturing method based on a stacked (build dup) system in which insulating layers and conductor layers are alternately stacked on an inner layer circuit board is known. The insulating layer is generally formed by curing a resin composition.

For example, patent document 1 describes a resin composition containing a liquid epoxy resin, a solid epoxy resin, an active ester curing agent, and an inorganic filler.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2020 and 029494.

Disclosure of Invention

Problems to be solved by the invention

However, in recent years, a lower dielectric loss tangent is required for a cured product of a resin composition for forming an insulating layer in the production of a multilayer printed wiring board.

In order to reduce the dielectric loss tangent, it is considered to include a component for reducing the dielectric loss tangent in the resin composition. As a result of the studies by the present inventors, when oxygen is present in the thermosetting of the resin composition layer, crosslinking of the component that lowers the dielectric loss tangent is suppressed by oxygen, and the curing reaction of the resin composition is hindered. Further, when the epoxy resin is volatilized in the thermal curing of the resin composition layer, crosslinkable components are reduced, which hinders the curing reaction. As a result, they found that: the crosslinking density of the cured product of the resin composition layer is low, and even if the dielectric loss tangent can be reduced, the insulation reliability of the cured product of the resin composition layer is poor.

The subject of the invention is to provide: a resin sheet from which a cured product having a low dielectric loss tangent and excellent insulation reliability can be obtained; a printed wiring board provided with an insulating layer formed using the resin sheet; a semiconductor device; a method for manufacturing a printed wiring board.

Means for solving the problems

The present inventors have made diligent studies to solve the above problems and, as a result, have found that: the present inventors have found that the above problems can be solved by using a predetermined support, further setting the solvent content in the resin composition forming the resin composition layer within a predetermined range, and further including any of (a-1) a volatile epoxy resin and (B) a radical polymerizable resin in the resin composition, and have completed the present invention.

That is, the present invention includes the following;

[1] a resin sheet comprising a support and, provided on the support, a resin composition layer comprising a resin composition,

wherein the oxygen permeability of the support measured by the method according to JIS K7126 is 20cc/m in an atmosphere of 23 ℃ and 50% RH²The number of times of day is less than or equal to day,

the amount of the solvent contained in the resin composition layer is 5% by mass or less,

the resin composition contains (A-1) any resin of volatile epoxy resin and (B) free radical polymerization resin;

[2]according to [1]The resin sheet, wherein the support has a water vapor transmission rate of 20g/m in an atmosphere of 40 ℃ and 90% RH as measured by JIS K7129²Day or less;

[3] the resin sheet according to [1] or [2], wherein the total content of the component (A-1) and the component (B) is 1 to 20% by mass, based on 100% by mass of the resin component;

[4] the resin sheet according to any one of [1] to [3], wherein the total content of the component (A-1), the component (B) and the solvent is 1 to 20 mass% inclusive, assuming that the resin component is 100 mass%;

[5] the resin sheet according to any one of [1] to [4], wherein the resin composition further contains (C) an inorganic filler;

[6] the resin sheet according to [5], wherein the content of the component (C) is 50% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass;

[7] a printed wiring board comprising an insulating layer formed of a cured product of a resin composition layer of the resin sheet described in any one of [1] to [6 ];

[8] a semiconductor device comprising the printed wiring board of [7 ];

[9] a method of manufacturing a printed wiring board, the method comprising in order:

(I) a step of laminating the resin sheet according to any one of [1] to [6] on the inner layer substrate so that the resin composition layer is bonded to the inner layer substrate,

(II) a step of forming an insulating layer by thermally curing the resin composition layer, and

(III) a step of peeling off the support.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a resin sheet capable of providing a cured product having a low dielectric loss tangent and excellent insulation reliability; a printed wiring board provided with an insulating layer formed using the resin sheet; a semiconductor device; a method for manufacturing a printed wiring board.

Detailed Description

The resin sheet, the printed wiring board including the insulating layer formed using the resin sheet, the semiconductor device, and the method for manufacturing the printed wiring board of the present invention will be described in detail below.

[ resin sheet ]

The resin sheet of the present invention is a resin sheet comprising a support and a resin composition layer comprising a resin composition provided on the support, wherein the oxygen permeability of the support measured by a method according to JIS K7126 is 20cc/m in an atmosphere of 23 ℃ and 50% RH²Day or less, the amount of the solvent contained in the resin composition layer is 5% by mass or less, and the resin composition contains any of (a-1) a volatile epoxy resin and (B) a radical polymerizable resin.

The cured product of the resin composition layer formed using the resin sheet of the present invention has a low dielectric loss tangent and excellent insulation reliability. In the present invention, a cured product having excellent adhesion to a copper foil and excellent adhesion to a copper foil after HAST can be obtained. Each layer constituting the resin sheet will be described in detail below.

< support >

The resin sheet of the present invention has a support. The oxygen permeability of the support measured by the method according to JIS K7126 was 20cc/m in an atmosphere of 23 ℃ and 50% RH²Day or less. In the thermal curing of the resin composition layer, when oxygen is present in the resin composition layer, the curing reaction of the resin composition is hindered. In addition, since the volatile epoxy resin may permeate through a support having a high oxygen permeability, the crosslinkable component may be reduced by volatilization of the epoxy resin during heat curing of the resin composition layer. As a result, the crosslinking density of the cured product of the resin composition layer is lowered, and the insulation reliability is poor. The resin sheet of the present invention has an oxygen permeability of 20cc/m in an atmosphere of 23 ℃ and 50% RH measured by a method according to JIS K7126²The support having a value of day or less can prevent oxygen from penetrating into the resin composition layer through the support. Further, the oxygen permeability is 20cc/m in an atmosphere of 23 ℃ and 50% RH²The support having a value of day or less can suppress volatilization of the epoxy resin contained in the resin composition layer, and can increase the crosslinking density of the cured product of the resin composition layer. Therefore, an insulating layer having a low dielectric loss tangent and excellent insulation reliability can be obtained.

The oxygen permeability of the support is 20cc/m in an atmosphere of 23 ℃ and 50% RH from the viewpoint of obtaining an insulating layer having a low dielectric loss tangent and excellent insulation reliability²Day or less, preferably 18cc/m²Day or less, more preferably 15cc/m²Day, 10cc/m or less²Day, 5cc/m or less²Day, 3cc/m or less²Day or less, or 1cc/m²Day or less. The lower limit is preferably 0cc/m²Day or more, preferably 0.01cc/m²Day or more, 0.05cc/m²Day or more. Here,% RH means relative humidity.

A specific method for measuring the oxygen permeability of the support can be carried out by using an oxygen permeability measuring apparatus (OX-TRAN 2/21 manufactured by MOCON Co., Ltd.) under an atmosphere of 23 ℃ and 50% RH according to JIS K7126 (isobaric method).

The water vapor permeability of the support is preferably 20g/m in an atmosphere of 40 ℃ and 90% RH from the viewpoint of obtaining an insulating layer having a low dielectric loss tangent and excellent insulation reliability²Day or less, preferably 18g/m²Day or less, more preferably 15g/m²Day, 10g/m or less²Day, 5g/m or less²Day, 3g/m or less²Day or less, or 1g/m²Day or less. The lower limit is preferably 0g/m²Day or more, preferably 0.01g/m²0.05g/m of day or more²Day or more.

A specific method for measuring the water vapor transmission rate of the support can be carried out by using a water vapor transmission rate measuring apparatus (PERMATRAN-W3/34, manufactured by MOCON) under an atmosphere of 40 ℃ and 90% RH in accordance with JIS K7129.

As the support, a support having an oxygen permeability of 20cc/m in an atmosphere of 23 ℃ and 50% RH measured by a method according to JIS K7126 can be used²A support of day or less. Examples of such a support include: the oxygen permeability is 20cc/m²A substrate of day or less, a support in which a release layer is laminated on a substrate, a support in which a barrier layer is laminated on a substrate, a support in which a release layer, a substrate, and a barrier layer are laminated in this order, and the like. In the case of a support having a barrier layer or a release layer laminated on a substrate, it is not necessary that the oxygen permeability of the substrate be 20cc/m²Day or less, provided that the oxygen permeability of the support obtained by laminating a barrier layer or a release layer on a substrate is 20cc/m²Day may be as follows.

Examples of the substrate 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.

When a film made of a plastic material is used as a substrate, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter, sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter, sometimes abbreviated as "PEN"), acrylic polymers such as polycarbonate (hereinafter, sometimes abbreviated as "PC") and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and polyethylene terephthalate is more preferred.

When a metal foil is used as the base material, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. As the copper foil, a foil formed of a single metal of copper may be used, and a foil formed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, or the like) may also be used.

Further, as the substrate, a substrate with a release layer having a release layer on a surface to be bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the release layer-equipped substrate include at least one release agent selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. The substrate having the release layer may be a commercially available one.

The thickness of the substrate is not particularly limited, but is preferably 5 μm or more, more preferably 10 μm or more, further preferably 20 μm or more, preferably 75 μm or less, further preferably 60 μm or less, further preferably 50 μm or less. When a substrate with a release layer is used, the thickness of the entire substrate with a release layer is preferably within the above range.

The support may also be provided with a barrier layer. By providing the barrier layer, the permeation of oxygen and water vapor can be suppressed. Examples of the barrier layer include an inorganic film and an organic film. Examples of the inorganic film include: metal foils of aluminum, copper, and the like; silicon dioxide vapor deposition film; a silicon nitride film; a silicon oxide film; magnesium oxide films, and the like. Further, examples of the organic film include: polyvinyl alcohol films, ethylene-vinyl alcohol copolymer films, polyvinylidene chloride films, and the like. The barrier layer may be composed of a multilayer barrier layer, or may be composed of an inorganic film and an organic film.

Examples of the method for forming the inorganic film include: chemical vapor deposition methods using heat, plasma, ultraviolet rays, or the like; physical vapor deposition methods such as vapor deposition and sputtering are used. Examples of the method for forming an organic film include: the organic compound can be formed by applying the organic compound to a substrate using a coating apparatus such as a die coater, comma coater, gravure coater, or bar coater.

The thickness of the barrier layer is preferably 0.05 μm or more, more preferably 0.1 μm or more, further preferably 0.15 μm or more, further preferably 10 μm or less, further preferably 5 μm or less, further preferably 3 μm or less, from the viewpoint of remarkably obtaining the effect of the present invention.

The substrate and the barrier layer may be joined to each other via an adhesive layer. As the adhesive that can be used for the adhesive layer, an adhesive that can bond the base material and the barrier layer can be used. Examples of such an adhesive include aqueous, solvent, hot melt, and active energy ray-curable adhesives that can be cured by an active energy ray such as ultraviolet rays.

The thickness of the adhesive layer is preferably 0.1 μm or more, more preferably 0.3 μm or more, further preferably 0.5 μm or more, further preferably 10 μm or less, further preferably 8 μm or less, further preferably 5 μm or less, from the viewpoint of remarkably obtaining the effect of the present invention.

The support may be provided with a release layer. By providing the release layer, the support and the resin composition layer can be easily separated from each other. Examples of the release agent that can be used for the release layer include at least one release agent selected from alkyd-based release agents, silicone-based release agents, polyurethane-based release agents, and olefin-based release agents. Among them, alkyd resin-based release agents are preferred from the viewpoint of remarkably obtaining the effects of the present invention.

The thickness of the release layer is preferably 10nm or more, more preferably 30nm or more, further preferably 50nm or more, preferably 1000nm or less, further preferably 500nm or less, further preferably 300nm or less, from the viewpoint of remarkably obtaining the effect of the present invention.

The total thickness of the support is preferably 10 μm or more, more preferably 15 μm or more, further preferably 20 μm or more, preferably 80 μm or less, more preferably 70 μm or less, further more preferably 60 μm or less, from the viewpoint of remarkably obtaining the effect of the present invention.

The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer of the base.

< layer of resin composition >

The resin sheet has a resin composition layer containing a resin composition, wherein the amount of a solvent contained in the resin composition layer is 5% by mass or less, and the resin composition contains any of (A-1) a volatile epoxy resin and (B) a radical polymerizable resin. By setting the amount of the solvent contained in the resin composition layer to 5% by mass or less, the solvent can be suppressed from remaining in the cured product of the resin composition layer, and therefore, the molecular spacing in the cured product can be suppressed from expanding and the crosslinking density can be suppressed from decreasing. This makes it difficult for ion migration to occur, and a cured product having excellent insulation reliability is formed. In addition, swelling (swelling) of the copper wiring pattern due to solvent evaporation can also be suppressed.

The resin composition contains any of the components (A-1) and (B) from the viewpoint of reducing the dielectric loss tangent. The resin composition may further contain, if necessary, (A-2) an epoxy resin other than the component (A-1), (C) an inorganic filler, (D) an organic filler, (E) a curing agent, (F) a curing accelerator, (G) a polymerization initiator, (H) a thermoplastic resin, (I) a flame retardant, and (J) other additives. Hereinafter, each component contained in the resin composition will be described in detail. In the present specification, the component (A-1) and the component (A-2) may be collectively referred to as the epoxy resin (A).

- (A-1) volatile epoxy resin-

The resin composition contains (A-1) a volatile epoxy resin as the component (A-1). However, when the resin composition contains the component (B), the limitation is not imposed. By containing (A-1) a volatile epoxy resin in the resin composition, the melt viscosity of the resin composition can be reduced. This suppresses an increase in the melt viscosity of the resin composition layer even when the inorganic filler (C) described later is contained in a large amount and the dielectric loss tangent is reduced. The component (A-1) may be used alone or in combination of two or more.

The volatile epoxy resin was judged as follows: when the weight loss ratio (weight loss ratio) of the epoxy resin was measured by heating from 30 ℃ to 550 ℃ at 10 ℃/min in air using a thermogravimetric differential thermal analyzer (TG-DTA apparatus), the volatile epoxy resin was one having a weight loss ratio of 3 mass% or more at 200 ℃. The specific method for determining the volatile epoxy resin is as follows: about 10mg (mass before heating) of the epoxy resin was weighed in an aluminum sample pan, and the weight (mass) of the sample at each temperature was measured by heating the epoxy resin from 30 ℃ to 550 ℃ at a heating rate of 10 ℃/min in an atmosphere of 200 mL/min air flow in an open state without a lid. From the obtained results, the weight loss ratio at 200 ℃ was calculated using the following formula: weight loss ratio (mass%) at 200 ℃ was 100 × (mass before heating-mass at 200 ℃)/mass before heating.

The weight loss at 200 ℃ of the volatile epoxy resin (A-1) is preferably 3% by mass or more, more preferably 3.5% by mass or more, still more preferably 4% by mass or more, still more preferably 20% by mass or less, yet more preferably 15% by mass or less, still more preferably 10% by mass or less, from the viewpoint of obtaining the desired effect of the present invention.

The component (a-1) preferably has 1 or more epoxy groups in 1 molecule, more preferably 2 or more epoxy groups in 1 molecule, and still more preferably 3 or more epoxy groups in 1 molecule, from the viewpoint of obtaining the desired effect of the present invention. 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 nonvolatile component of the (a-1) component.

The component (A-1) includes a component (A-1) which is liquid at a temperature of 20 ℃ and a component (A-1) which is solid at a temperature of 20 ℃. From the viewpoint of obtaining the desired effect of the present invention, the component (A-1) is preferably in a liquid state.

As the component (A-1), the above-mentioned epoxy resin having a weight loss ratio of 3 mass% or more can be used. The epoxy resin is preferably one having a cyclic skeleton. Examples of the cyclic structure include an alicyclic structure and an aromatic ring structure. Examples of the alicyclic structure include cyclohexane ring, cyclopentane ring, cycloheptane ring, cyclooctane ring and the like, and cyclohexane ring is preferable. Examples of the aromatic ring structure include a benzene ring, a naphthalene ring, an anthracene ring and the like, and a benzene ring is preferred.

Specific examples of the component (A-1) include "ZX 1658 GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resin) manufactured by NIPPON STEEL Chemical & Material Co., Ltd.; "EX-721" (liquid diglycidyl ether phthalate type epoxy resin) manufactured by Nagase ChemteX; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Dailuo corporation; "ZX 1658" (liquid 1, 4-glycidylcyclohexane-type epoxy resin) available from Nippon iron chemical Co., Ltd. These may be used alone or in combination of two or more.

The epoxy equivalent of the component (A-1) is preferably 50 g/eq.to 5000 g/eq.more preferably 50 g/eq.to 3000 g/eq.further preferably 80 g/eq.to 2000 g/eq.further more preferably 110 g/eq.to 1000 g/eq.. When the amount is within this range, the crosslinking density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of the epoxy group. The epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the component (A-1) is preferably 100 to 5000, more preferably 200 to 3000, and still more preferably 250 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.

From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, the content of the component (a-1) is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and still more preferably 1 mass% or more, with 100 mass% of nonvolatile components in the resin composition. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit of the content of the epoxy resin is preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably 3% by mass or less. In the present invention, the content of each component in the resin composition is a value when the nonvolatile component in the resin composition is 100 mass%, unless otherwise specified.

- (A-2) epoxy resin other than the (A-1) component-

The resin composition may further contain, as optional components, (a-2): an epoxy resin other than the component (A-1). The component (A-2) is an epoxy resin having a weight loss rate of less than 3% by mass at 200 ℃.

Examples of the component (A-2) include: a biscresol (bixylenol) 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 trisphenol type epoxy resin, a naphthol novolac (naphthol novolac) 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 glycidylamine type epoxy resin, a glycidyl ester 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, an alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol novolac type epoxy resin, a naphthol type epoxy resin, a styrene type epoxy resin, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, and the like. The epoxy resin may be used alone or in combination of two or more.

The component (A-2) is preferably an epoxy resin containing 2 or more epoxy groups in 1 molecule. 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 nonvolatile component of the (a-2) component.

The component (A-2) includes an epoxy resin which is liquid at a temperature of 20 ℃ (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin which is solid at a temperature of 20 ℃ (hereinafter sometimes referred to as "solid epoxy resin"). The component (a-2) may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin, and from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferable to contain a combination of a liquid epoxy resin and a solid epoxy resin.

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

The solid epoxy resin is preferably a bisxylenol type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol 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, a tetraphenylethane type epoxy resin, and more preferably a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, or a bisphenol AF type epoxy resin.

Specific examples of the solid epoxy resin include: HP4032H (naphthalene epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200", "HP-7200 HH" and "HP-7200H" (dicyclopentadiene type epoxy resins) manufactured by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" and "HP 6000" (naphthylene ether type epoxy resins) manufactured by DIC corporation; EPPN-502H (trisphenol type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by japan chemicals); "NC 3000H", "NC 3000L" and "NC 3100" (biphenyl type epoxy resin) manufactured by japan chemical company; ESN475V (naphthol type epoxy resin) manufactured by Nippon iron chemical Co., Ltd; ESN485 (naphthol novolac type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "YX 4000H", "YX 4000", "YL 6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical company; "YX 4000 HK" (bisphenol type epoxy resin) manufactured by Mitsubishi chemical corporation; YX8800 (anthracene-based epoxy resin) available from Mitsubishi chemical corporation; PG-100 and CG-500 manufactured by Osaka gas chemical company; "YL 7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL 7800" (fluorene-based epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 1010" (solid bisphenol a type epoxy resin) manufactured by mitsubishi chemical corporation; "jER 1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation, and the like. These may be used alone or in combination of two or more.

The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.

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

Specific examples of the liquid epoxy resin include: "HP 4032", "HP 4032D" and "HP 4032 SS" (naphthalene epoxy resins) manufactured by DIC; "828 US", "jER 828 EL", "825", "EPIKOTE 828 EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi chemical company; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical corporation; "630" and "630 LSD" (glycidyl amine type epoxy resins) manufactured by mitsubishi chemical corporation; "ZX 1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon iron chemical Co., Ltd.; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daiiluo Co., Ltd. These may be used alone or in combination of two or more.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (a-2), the amount ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 1: 1-1: 20, more preferably 1: 1.5-1: 15, particularly preferably 1: 2-1: 10. by making the amount ratio of the liquid epoxy resin to the solid epoxy resin within the range, the desired effects of the present invention can be remarkably obtained. Further, when the resin sheet is used in the form of a resin sheet, appropriate adhesiveness can be provided. In addition, when the resin sheet is used in the form of a resin sheet, sufficient flexibility is obtained, and handling properties are improved. Further, a cured product having a sufficient breaking strength can be usually obtained.

The epoxy equivalent of the component (A-2) is preferably 50 g/eq.about 5000g/eq, more preferably 50 g/eq.about 3000g/eq, still more preferably 80 g/eq.about 2000g/eq, and still more preferably 110 g/eq.about 1000g/eq. When the amount is within this range, the crosslinking density of the cured product of the resin composition layer becomes sufficient, and an insulating layer having a small surface roughness can be provided.

The weight average molecular weight (Mw) of the component (A-2) is preferably 100 to 5000, more preferably 200 to 3000, and still more preferably 250 to 1500, from the viewpoint of remarkably obtaining the desired effect of the present invention.

From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, the content of the component (a-2) is preferably 1 mass% or more, more preferably 3 mass% or more, and still more preferably 5 mass% or more, assuming that the nonvolatile component in the resin composition is 100 mass%. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit of the content of the epoxy resin is preferably 40% by mass or less, more preferably 30% by mass or less, particularly preferably 20% by mass or less.

When the component (A-1) and the component (A-2) are used in combination, the ratio of the amounts thereof (the component (A-1) (the component (A-2)) is preferably 1: 1-1: 20, more preferably 1: 1.5-1: 15, particularly preferably 1: 2-1: 10.

- (B) radical polymerizable resin-

The resin composition contains (B) a radical polymerizable resin as the component (B). However, when the resin composition contains the component (A-1), the limitation is not imposed. By adding the radical polymerizable resin (B) to the resin composition, a cured product having a low dielectric loss tangent can be obtained.

As the component (B), a resin having a radical polymerizable unsaturated group can be used. The radical polymerizable group is a group having an olefinic double bond which exhibits curability by irradiation with active energy rays such as ultraviolet rays or heat. Examples of such groups include: vinyl group, vinylphenyl group, acryloyl group, methacryloyl group, maleimide group, fumaryl group (fumaroyl group), and maleoyl group (maleoyl group), and at least one selected from vinylphenyl group, acryloyl group, and methacryloyl group is preferable. Here, the acryloyl group and methacryloyl group are sometimes collectively referred to as "(meth) acryloyl group". Further, vinylphenyl means a group having the structure shown below:

[ chemical formula 1]

(. sup. represents a connecting bond).

From the viewpoint of obtaining a cured product having a low dielectric loss tangent, component (B) preferably has 2 or more radical polymerizable unsaturated groups per 1 molecule.

The component (B) preferably has a cyclic structure from the viewpoint of obtaining a cured product having a low dielectric loss tangent. As the cyclic structure, a divalent cyclic group is preferred. The divalent cyclic group may be any of an alicyclic structure-containing cyclic group and an aromatic ring structure-containing cyclic group. In addition, there may be a plurality of divalent cyclic groups.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the divalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, further preferably a 5-membered ring or more, preferably a 20-membered ring or less, further preferably a 15-membered ring or less, further preferably a 10-membered ring or less. The divalent cyclic group may have a monocyclic structure or a polycyclic structure.

The ring in the divalent cyclic group may be a skeleton of the ring formed of hetero atoms in addition to carbon atoms. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like, and an oxygen atom is preferred. The number of heteroatoms in the ring may be 1 or more, and may be 2 or more.

Specific examples of the divalent cyclic group include the following divalent groups (i) to (xiii):

[ chemical formula 2]

(in the divalent groups (xii), (xiii), R¹、R²、R⁵、R⁶、R⁷、R¹¹And R¹²Each independently represents a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, R³、R⁴、R⁸、R⁹And R¹⁰Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group).

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 6 or less carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is preferred. As R¹、R²、R⁵、R⁶、R⁷、R¹¹And R¹²Preferably, it represents a methyl group. As R³、R⁴、R⁸、R⁹And R¹⁰Preferably a hydrogen atom or a methyl group.

In addition, the divalent cyclic group may combine a plurality of divalent cyclic groups. Specific examples of the case of combining divalent cyclic groups include divalent cyclic groups represented by the following formula (a), i.e., divalent groups (a):

[ chemical formula 3]

(in the formula (a), R²¹、R²²、R²⁵、R²⁶、R²⁷、R³¹、R³²、R³⁵And R³⁶Each independently represents a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, R²³、R²⁴、R²⁸、R²⁹、R³⁰、R³³And R³⁴Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group; n and m represent an integer of 0 to 300; however, except for the case where one of n and m is 0).

R²¹、R²²、R³⁵And R³⁶With R in the divalent radical (xii)¹The meaning is the same. R²³、R²⁴、R³³And R³⁴With R in the divalent radical (xii)³The meaning is the same. R²⁵、R²⁶、R²⁷、R³¹And R³²And R in formula (xiii)⁵The meaning is the same. R²⁸、R²⁹And R³⁰And R in formula (xiii)⁸The meaning is the same.

n and m represent an integer of 0 to 300. However, the case where one of n and m is 0 is excluded. N and m are preferably integers of 1 to 100, more preferably integers of 1 to 50, and still more preferably integers of 1 to 10. n and m may be the same or different.

As the divalent cyclic group, a divalent group (x), a divalent group (xi) or a divalent group (a) is preferable, and a divalent group (x) or a divalent group (a) is more preferable.

The divalent cyclic group may have a substituent. Examples of such a substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, an oxo group (carbonyl group), and the like, and an alkyl group is preferable.

The radical polymerizable unsaturated group may be bonded directly to the divalent cyclic group or may be bonded via a divalent linking group. Examples of the divalent linking group include alkylene, alkenylene, arylene, heteroarylene, -C (═ O) O-, -NHC (═ O) -, -NC (═ O) N-, -NHC (═ O) O-, -C (═ O) -, -S-, -SO-, -NH-, and a plurality of these groups may be combined. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, still more preferably an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 4 carbon atoms. The alkylene group may be any of linear, branched, and cyclic. Examples of the alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1, 1-dimethylethylene, and methylene, ethylene, and 1, 1-dimethylethylene are preferable. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and still more preferably an alkenylene group having 2 to 5 carbon atoms. The arylene and heteroarylene group is preferably an arylene or heteroarylene group having 6 to 20 carbon atoms, more preferably an arylene or heteroarylene group having 6 to 10 carbon atoms. As the divalent linking group, an alkylene group is preferable, and among them, a methylene group and a1, 1-dimethylethylene group are more preferable.

(B) The component (B) is preferably represented by the following formula (1):

[ chemical formula 4]

(in the formula (1), R⁵¹And R⁵⁴Each independently represents a radical polymerizable unsaturated group, R⁵²And R⁵³Each independently represents a divalent linking group; ring B represents a divalent cyclic group).

R⁵¹And R⁵⁴Each independently represents a radical polymerizable unsaturated group, preferably a vinylphenyl group or a (meth) acryloyl group.

R⁵²And R⁵³Each independently represents a divalent linking group. As the divalent linking group, the same as the above-mentioned divalent linking group means.

Ring B represents a divalent cyclic group. The ring B is the same as the above-mentioned divalent cyclic group.

Ring B may have a substituent. The substituent is the same as the substituent that the above-mentioned divalent cyclic group may have.

Specific examples of the component (B) are shown below, but the present invention is not limited thereto;

[ chemical formula 5]

(n1 has the same meaning as n in the formula (a) and m1 has the same meaning as m in the formula (a)).

(B) As the component (B), commercially available products such as "OPE-2 St" available from Mitsubishi gas chemical company, "A-DOG" available from New Mitsubishi chemical industry, and "DCP-A" available from KyowｃA chemical company can be used. (B) The components can be used singly or in combination.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the number average molecular weight of the component (B) is preferably 3000 or less, more preferably 2500 or less, further preferably 2000 or less and 1500 or less. The lower limit is preferably 100 or more, more preferably 300 or more, still more preferably 500 or more and 1000 or more. The number average molecular weight is a polystyrene-equivalent number average molecular weight measured by Gel Permeation Chromatography (GPC).

From the viewpoint of remarkably obtaining the effect of the present invention, the content of the component (B) is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, and further more preferably 0.5 mass% or more, assuming that the nonvolatile content in the resin composition is 100 mass%. The upper limit is preferably 30% by mass or less, more preferably 15% by mass or less, and still more preferably 5% by mass or less.

The total content of the component (A-1) and the component (B) is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 4% by mass or more, preferably 20% by mass or less, further preferably 15% by mass or less, further preferably 10% by mass or less, based on 100% by mass of the resin component, from the viewpoint of remarkably obtaining the effect of the present invention. Here, the resin component means a component other than (C) the inorganic filler and (D) the organic filler.

The total content of the component (a-1), the component (B), and the solvent contained in the resin composition layer is preferably 1 mass% or more, more preferably 3 mass% or more, further preferably 5 mass% or more, preferably 25 mass% or less, further preferably 20 mass% or less, further preferably 15 mass% or less, based on 100 mass% of the resin component, from the viewpoint of remarkably obtaining the effect of the present invention.

- (C) inorganic filling materials-

The resin composition may further contain (C) an inorganic filler as an optional component.

As a material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler 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, zirconium phosphate, zirconium phosphotungstate, and the like. Among them, silica is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as the silica, spherical silica is preferable. (C) The components can be used singly or in combination.

Examples of commercially available products of component (C) include: "UFP-30" manufactured by Denka corporation; "SP 60-05" and "SP 507-05" manufactured by Nissi iron-alloy materials Corp; "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C" manufactured by Admatech (Admatech); "Silfil (シルフィル) NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Deshan (Tokuyama); "SC 2500 SQ", "SO-C4", "SO-C2" and "SO-C1" manufactured by Yatoma corporation.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the average particle size of the component (C) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 5 μm or less, more preferably 2 μm or less, and still more preferably 1 μm or less.

(C) The average particle diameter of the component can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size is measured as an average particle size. For the measurement sample, a sample obtained by weighing 100mg of the inorganic filler and 10g of methyl ethyl ketone into a vial and dispersing them by ultrasonic waves for 10 minutes can be used. The volume-based particle size distribution of the inorganic filler (C) was measured in a flow cell (flow cell) using a laser diffraction type particle size distribution measuring apparatus with the wavelengths of the light source used being 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, Ltd.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the specific surface area of the component (C) is preferably 1m²More than g, preferably 2m²More than g, particularly preferably 3m²More than g. The upper limit is not particularly limited, but is preferably 60m²Less than 50 m/g²Less than or equal to 40 m/g²The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area can be obtained as follows: according to the BET method, nitrogen gas was adsorbed onto the surface of a sample using a specific surface area measuring apparatus (Macsorb HM-1210, Mountech corporation), and the specific surface area was calculated by the BET multipoint method.

From the viewpoint of improving moisture resistance and dispersibility, component (C) is preferably treated with a surface-treating agent. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilicon azane compounds, titanate coupling agents, and the like. The surface treatment agent may be used alone or in combination of two or more kinds.

Examples of commercially available surface treatment agents include: "KBM 403" (3-glycidoxypropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "KBM 803" (3-mercaptopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "KBE 903" (3-aminopropyltriethoxysilane) manufactured by shin-Etsu chemical industries, "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "SZ-31" (hexamethyldisilazane) manufactured by shin-Etsu chemical industries, "KBM 103" (phenyltrimethoxysilane) manufactured by shin-Etsu chemical industries, "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by shin-Etsu chemical industries, and "KBM-7103" (3,3, 3-trifluoropropyltrimethoxysilane) manufactured by shin-Etsu chemical industries.

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a predetermined range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent, more preferably 0.2 to 3 parts by mass of the surface treatment agent, and still more preferably 0.3 to 2 parts by mass of the surface treatment agent.

The degree of surface treatment by 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 amount of carbon per unit surface area of the inorganic filler is preferably 0.02mg/m²Above, preferably 0.1mg/m²The above, more preferably 0.2mg/m²The above. On the other hand, from the viewpoint of suppressing an increase in melt viscosity of the resin varnish and melt viscosity in the form of a sheet, it is preferably 1mg/m²The concentration is preferably 0.8mg/m or less²It is more preferably 0.5m or lessg/m²The following.

(C) The amount of carbon per unit surface area of the component (a) can be measured after the inorganic filler after the surface treatment is subjected to a cleaning treatment with a solvent such as Methyl Ethyl Ketone (MEK). Specifically, a sufficient amount of MEK was added as a solvent to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning was performed at 25 ℃ for 5 minutes. After removing the supernatant liquid and drying the solid components, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, Ltd., can be used.

From the viewpoint of reducing the dielectric loss tangent, the content of the component (C) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, based on 100% by mass of nonvolatile components in the resin composition.

When the content (mass%) of the component (C) is C and the content (mass%) of the component (a-1) is a1 when the nonvolatile content in the resin composition is 100 mass%, the C/a1 is preferably 10 or more, more preferably 20 or more, further preferably 30 or more, preferably 90 or less, further preferably 85 or less, further preferably 80 or less, from the viewpoint of remarkably obtaining the effects of the present invention.

When the content (mass%) of the component (B) is B when the nonvolatile content in the resin composition is 100 mass%, c/B is preferably 30 or more, more preferably 40 or more, further preferably 50 or more, preferably 80 or less, more preferably 70 or less, and further more preferably 60 or less, from the viewpoint of remarkably obtaining the effect of the present invention.

- (D) organic filling materials

The resin composition (photosensitive resin composition) may further contain (D) an organic filler as an optional component. (D) Since the organic filler exhibits flexibility, the stress of the cured product of the resin composition can be dispersed, and as a result, the insulation reliability can be improved.

Examples of the component (D) include polyurethane fine particles, rubber particles, polyamide fine particles, and silicone particles.

As the polyurethane fine particles, commercially available ones can be used, and examples thereof include "MM-101 SW", "MM-101 SWA", "MM-101 SM", "MM-101 SMA" and "MM-110 SMA" manufactured by Industrial Co.

The rubber particles may be any particles of a resin that exhibits rubber elasticity and is insoluble and infusible in an organic solvent by chemical crosslinking treatment. Preferable examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, and the like. The core-shell type rubber particles are rubber particles having a core layer and a shell layer, and examples thereof include: and rubber particles having a 2-layer structure in which the shell layer of the outer layer is made of a glassy polymer and the core layer of the inner layer is made of a rubbery polymer, or a 3-layer structure in which the shell layer of the outer layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glassy polymer layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). For the rubber particles, 2 or more kinds may be used in combination. Specific examples of the core-shell type rubber particles include: "IM 401-4-14" by AICA industries; "AC 3832", "AC 3816N", "AC 3401N", "IM-401 modified by Gantsu Kasei Corp."; "METABLEN KW-4426" manufactured by Mitsubishi Rayon, Inc. Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include "XER-91" (average particle diameter of 0.5 μm) manufactured by JSR Corp. Specific examples of the crosslinked Styrene Butadiene Rubber (SBR) particles include "XSK-500" (average particle diameter of 0.5 μm) manufactured by JSR corporation. Specific examples of the acrylic rubber particles include "METABLEN W300A" (average particle diameter 0.1 μm) and "W450A" (average particle diameter 0.2 μm) manufactured by Mitsubishi corporation.

As the polyamide fine particles, fine particles having an amide bond-containing resin of 50 μm or less can be used, and examples thereof include aliphatic polyamides such as nylon, aromatic polyamides such as Kevlar (Kevlar), and polyamide-imides. As the polyamide fine particles, commercially available ones can be used, and examples thereof include "VESTOSINT 2070" manufactured by Daicel-Huels; "SP 500" manufactured by Dongli corporation, and the like.

(D) The average particle size of the component (A) is preferably at least 0.005 μm, more preferably at least 0.2 μm, still more preferably at most 1 μm, most preferably at most 0.6. mu.m. (D) The average particle diameter of the component can be measured by a dynamic light scattering method. (D) The average particle diameter of the component can be measured, for example, as follows: the organic filler is uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, a particle size distribution of the organic filler is prepared on a mass basis using a dense particle size analyzer (for example, FPAR-1000 available from Otsuka Denshi Co., Ltd.), and the median particle size is measured as an average particle size.

From the viewpoint of remarkably obtaining the effect of the present invention, the content of the component (D) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, preferably 5% by mass or less, further preferably 3% by mass or less, further preferably 1% by mass or less, when the nonvolatile content of the resin composition is set to 100% by mass.

- (E) curing agent-

The resin composition may further contain (E) a curing agent as an optional component. (E) The component (B) generally has a function of curing the resin composition by reacting with the component (A). (E) One of the components may be used alone, or two or more of them may be used in combination at an arbitrary ratio.

As the component (E), a compound capable of reacting with the component (a) to cure the resin composition can be used, and examples thereof include an active ester-based curing agent, a phenol-based curing agent, a benzoxazine-based curing agent, a carbodiimide-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, and a cyanate-based curing agent. Among them, from the viewpoint of remarkably obtaining the effect of the present invention, any of an active ester-based curing agent, a phenol-based curing agent, a benzoxazine-based curing agent, and a carbodiimide-based curing agent is preferable, and any of an active ester-based curing agent, a phenol-based curing agent, and a carbodiimide-based curing agent is more preferable.

The active ester-based curing agent includes a curing agent having 1 or more active ester groups in 1 molecule. Among them, as the active ester-based curing agent, compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, are preferable. The active ester-based curing agent is preferably a compound obtained by a 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, and pyromellitic acid.

Examples of the phenol compound or naphthol compound include: hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac (phenol novolac), and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing 2 molecules of phenol with 1 molecule of dicyclopentadiene.

Preferred specific examples of the active ester-based curing agent include: 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 phenol novolac resin, and an active ester compound containing a benzoyl compound of a phenol novolac resin. Among them, preferred are active ester compounds having a naphthalene structure and active ester compounds having a dicyclopentadiene type diphenol structure. The "dicyclopentadiene type diphenol structure" means a divalent structure formed from phenylene-dicyclopentyl (ジシクロペンチレン) -phenylene.

As commercially available products of the active ester-based curing agent, examples of the active ester compound having a dicyclopentadiene type diphenol structure include "EXB 9451", "EXB 9460S", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65 TM", "EXB-8000L-65 TM" (manufactured by DIC Co., Ltd.); examples of the active ester compound having a naphthalene structure include "HPC-8150-60T", "HPC-8150-62T", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T", "EXB 9416-70 BK" (manufactured by DIC); examples of the active ester compound containing an acetylated novolak resin include "DC 808" (manufactured by Mitsubishi chemical corporation); examples of the active ester compound containing a phenolic novolak resin benzoyl compound include "YLH 1026" (manufactured by Mitsubishi chemical corporation); examples of the active ester-based curing agent for the acetylated novolak resin include "DC 808" (manufactured by mitsubishi chemical corporation); examples of the active ester-based curing agent for the benzoylate of the novolak resin include "YLH 1026" (manufactured by Mitsubishi chemical corporation), "YLH 1030" (manufactured by Mitsubishi chemical corporation), and "YLH 1048" (manufactured by Mitsubishi chemical corporation).

The phenol-based curing agent includes a curing agent having 1 or more, preferably 2 or more hydroxyl groups bonded to an aromatic ring (benzene ring, naphthalene ring, etc.) in 1 molecule. Among them, compounds having a hydroxyl group bonded to a benzene ring are preferred. In addition, a phenol-based curing agent having a phenolic structure (novolak structure) is preferable from the viewpoint of heat resistance and water resistance. In addition, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferred, and a phenol-based curing agent having a triazine skeleton is more preferred. In particular, a phenol novolac (phenolic novolac) curing agent containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance and adhesion.

Specific examples of the phenol-based curing agent (phenol-based curing agent) and the naphthol-based curing agent include: MEH-7700, MEH-7810, MEH-7851, MEH-8000H, manufactured by Ming and Cheng chemical company; "NHN", "CBN" and "GPH" manufactured by Nippon chemical Co., Ltd.; "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495V", "SN-375", "SN-395", manufactured by Nissan chemical materials Ltd; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165", manufactured by DIC; GDP-6115L, GDP-6115H, ELPC75, etc., manufactured by Rongche chemical Co.

Specific examples of the benzoxazine-based curing agent include "ODA-BOZ" manufactured by JFE chemical, the "HFB 2006M" manufactured by SHOWA HIGHER POLYMER, and "P-d" and "F-a" manufactured by SiCOH CHEMICAL INDUSTRIAL CORPORATION.

Specific examples of the carbodiimide-based curing agent include "V-03", "V-05", "V-07", manufactured by Nisshinbo chemical Co., Ltd; stabaxol (registered trademark) P manufactured by Rhein Chemie, Inc.

Examples of the acid anhydride-based curing agent include a curing agent having 1 or more acid anhydride groups in 1 molecule. Specific examples of the acid anhydride-based curing agent include: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3', 4,4' -diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (trimellitic anhydride ester), styrene-maleic acid resin obtained by copolymerizing styrene with maleic acid, and other polymer-type acid anhydrides. As the acid anhydride-based curing agent, commercially available products such as "MH-700" manufactured by Nissian chemical Co., Ltd.

The amine-based curing agent includes those having 1 or more amino groups in 1 molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, and among them, aromatic amines are preferable from the viewpoint of exhibiting the desired effects of the present invention. The amine-based curing agent is preferably a primary or secondary amine, more preferably a primary amine. Specific examples of the amine-based curing agent include: 4,4 '-methylenebis (2, 6-dimethylaniline), diphenyldiaminosulfone, 4' -diaminodiphenylmethane, 4 '-diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4 '-diaminodiphenyl ether, 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane, 3-dimethyl-5, 5-diethyl-4, 4-diphenylmethanediamine, 2-bis (4-aminophenyl) propane, diphenylmethanesulphone, 4 '-diaminodiphenylmethanesulphone, 4' -diaminodiphenylsulphone, 3 '-diaminodiphenylsulphone, m-phenylenediamine, 2-bis (4-aminophenyl) propane, diphenylmethanesulphone, 4-methyl-4, 3' -diaminodiphenylmethanesulphone, 2 '-diaminodiphenylmethanesulphone, 2' -diaminobenzenesulphone, 2,3 '-diaminobenzenesulphone, 2-bis (4-amino-4-diaminobenzenesulphone), 2-benzenesulphone, 4-diaminobenzenesulphone, 4-diaminobenzenesulphone, 2, 4-benzenesulphone, 2' -diaminobenzenesulphone, 2,4, 2,4 '-diaminobenzenesulphone, 4, 2, 4' -diaminobenzenesulphone, 2,4, 2,4, 2,4, 2, and so, 4, 2,2, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone and the like. As the amine-based curing agent, commercially available ones can be used, and examples thereof include "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARDA-B", "KAYAHARDA-S" manufactured by Nippon chemical company, and "EPICURE W" manufactured by Mitsubishi chemical company.

Examples of the cyanate ester-based curing agent include: bifunctional cyanate resins such as bisphenol a dicyanate, polyphenol cyanate, oligo (3-methylene-1, 5-phenylene cyanate), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyl dicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate ester) phenylpropane, 1-bis (4-cyanate ester phenylmethane), bis (4-cyanate ester-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate ester-phenyl-1- (methylethylidene)) benzene, bis (4-cyanate ester-phenyl) sulfide, and bis (4-cyanate ester-phenyl) ether; polyfunctional cyanate ester resins derived from phenol novolac resins (phenol novolac) and cresol novolac resins (cresol novolac), and the like; prepolymers obtained by triazinating a part of these cyanate ester resins, and the like. Specific examples of the cyanate ester-based curing agent include "PT 30" and "PT 60" (both phenol novolac-type polyfunctional cyanate ester resins) manufactured by Lonza Japan; "ULL-950S" (polyfunctional cyanate ester resin); "BA 230" and "BA 230S 75" (prepolymers in which a part or all of bisphenol A dicyanate is triazinated to form a trimer).

From the viewpoint of remarkably obtaining the effect of the present invention, the content of the (E) curing agent is preferably 1 mass% or more, more preferably 5 mass% or more, further preferably 10 mass% or more, preferably 25 mass% or less, further preferably 20 mass% or less, further preferably 15 mass% or less, with respect to 100 mass% of nonvolatile components in the resin composition.

When the number of epoxy groups in the component (A) is 1, the number of active groups in the curing agent (E) is preferably at least 0.1, more preferably at least 0.3, still more preferably at least 0.5, still more preferably at most 2, yet more preferably at most 1.8, still more preferably at most 1.5. The term "the number of epoxy groups in the component (a)" means a total value of all the values obtained by dividing the mass of nonvolatile components of the component (a) present in the resin composition by the epoxy equivalent weight. The term "the number of active groups of the (E) curing agent" means a total of all the values obtained by dividing the mass of nonvolatile components of the (E) curing agent present in the resin composition by the equivalent of the active groups. When the number of epoxy groups of the component (a) is 1, the number of active groups of the curing agent (E) is in the above range, whereby the desired effects of the present invention can be remarkably obtained.

When the number of epoxy groups in the component (A-1) is 1, the number of active groups in the curing agent (E) is preferably at least 0.01, more preferably at least 0.05, still more preferably at least 0.1, still more preferably at most 15, still more preferably at most 10, still more preferably at most 8. Here, "the number of epoxy groups of the component (A-1)" means a total value of all the values obtained by dividing the mass of nonvolatile components of the component (A-1) present in the resin composition by the epoxy equivalent weight. When the number of epoxy groups of the component (A-1) is 1, the number of active groups of the curing agent (E) is in the above range, whereby the desired effects of the present invention can be remarkably obtained.

- (F) curing accelerators-

The resin composition may further contain (F) a curing accelerator as an optional component in addition to the above components.

Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among them, preferred are phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators, and more preferred are amine-based curing accelerators, imidazole-based curing accelerators and metal-based curing accelerators. The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo [5.4.0] undecene, with 4-dimethylaminopyridine and 1, 8-diazabicyclo [5.4.0] undecene being preferred.

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, salts thereof with a group selected from the group consisting of, 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 isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 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, 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based curing accelerator, commercially available products such as "P200-H50" manufactured by Mitsubishi chemical company can be used.

Examples of the guanidine-based 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, and dicyandiamide and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene are preferred.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. 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 (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the component (F) is preferably 0.01 mass% or more, more preferably 0.03 mass% or more, further preferably 0.05 mass% or more, preferably 0.3 mass% or less, further preferably 0.2 mass% or less, further preferably 0.1 mass% or less, with respect to 100 mass% of nonvolatile components in the resin composition.

- (G) polymerization initiator

The resin composition may further contain (G) a polymerization initiator as an optional component in addition to the above components. (G) Component (B) generally has a function of promoting crosslinking of the radical polymerizable unsaturated group in component (B). (G) One kind of the component may be used alone, or two or more kinds may be used in combination.

Examples of the polymerization initiator (G) include peroxides such as t-butylcumyl peroxide, t-butyl peroxyacetate, α' -di (t-butylperoxy) diisopropylbenzene, t-butyl peroxylaurate, t-butyl peroxy2-ethylhexanoate, t-butyl peroxyneodecanoate, and t-butyl peroxybenzoate.

Examples of commercially available products of the polymerization initiator (G) include: "PERBUTYL C", "PERBUTYL A", "PERBUTYL P", "PERBUTYL L", "PERBUTYL O", "PERBUTYL ND", "PERBUTYLZ", "PERCUTYLP", "PERCUTYLD", and the like, manufactured by RIGAL OIL CORPORATION.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the (G) polymerization initiator is preferably 0.01 mass% or more, more preferably 0.02 mass% or more, further preferably 0.03 mass% or more, preferably 0.3 mass% or less, further preferably 0.2 mass% or less, further preferably 0.1 mass% or less, with respect to 100 mass% of nonvolatile components in the resin composition.

- (H) thermoplastic resin-

The resin composition may further contain (H) a thermoplastic resin as an optional component in addition to the above components.

Examples of the thermoplastic resin of component (H) include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polycarbonate resins, polyetheretherketone resins, and polyester resins. Among them, phenoxy resins are preferred from the viewpoint of remarkably obtaining the desired effect of the present invention. The thermoplastic resin may be used alone or in combination of two or more.

Examples of the phenoxy resin include phenoxy resins having 1 or more kinds of skeletons selected from a bisphenol a skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenol (novolac) skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a 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 phenoxy resins having a bisphenol A skeleton) manufactured by Mitsubishi chemical corporation; "YX 8100" (phenoxy resin containing bisphenol S skeleton) manufactured by Mitsubishi chemical corporation; "YX 6954" (phenoxy resin containing bisphenol acetophenone skeleton) manufactured by Mitsubishi chemical company; "FX 280" and "FX 293" available from Nippon iron chemical materials; "YL 7500BH 30", "YX 6954BH 30", "YX 7553BH 30", "YL 7769BH 30", "YL 6794", "YL 7213", "YL 7290" and "YL 7482" manufactured by Mitsubishi chemical corporation; and so on.

Examples of the polyvinyl acetal resin include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of the polyvinyl acetal resin include "Denka butyl ral 4000-2", "Denka butyl ral 5000-A", "Denka butyl ral 6000-C", "Denka butyl ral 6000-EP" manufactured by the electrochemical industries; S-LEC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series, and the like, manufactured by Water accumulation chemical industries.

Specific examples of the polyimide resin include "RIKACOAT SN 20" and "RIKACOAT PN 20" manufactured by shin-shin chemical & chemical company. Specific examples of the polyimide resin include modified polyimides such as linear polyimides obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimides described in jp 2006-37083 a), polyimides containing a polysiloxane skeleton (polyimides described in jp 2002-12667 a, jp 2000-319386 a and the like).

Specific examples of the polyamide-imide resin include "VYLOMAX HR11 NN" and "VYLOMAX HR16 NN" manufactured by tokyo corporation. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS 9100" and "KS 9300" (polyamide-imide having a polysiloxane skeleton) manufactured by hitachi chemical company.

Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by sumitomo chemical corporation.

Specific examples of the polysulfone resin include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the weight average molecular weight (Mw) of the (H) thermoplastic resin is preferably 8000 or more, more preferably 10000 or more, particularly preferably 20000 or more, preferably 70000 or less, more preferably 60000 or less, particularly preferably 50000 or less.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the content of the (H) thermoplastic resin is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, further preferably 0.3 mass% or more, preferably 5 mass% or less, further preferably 3 mass% or less, further preferably 1 mass% or less, with respect to 100 mass% of nonvolatile components in the resin composition.

(I) flame retardants-

The resin composition may further contain (I) a flame retardant as an optional component in addition to the above components.

Examples of the flame retardant (I) include phosphazene compounds, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, organosilicon flame retardants, and metal hydroxides, and phosphazene compounds are preferred. One kind of flame retardant may be used alone, or two or more kinds may be used in combination.

The phosphazene compound is not particularly limited as long as it is a cyclic compound having nitrogen and phosphorus as constituent elements, and is preferably a phosphazene compound having a phenolic hydroxyl group.

Specific examples of the phosphazene compound include "SPH-100", "SPS-100", "SPB-100" and "SPE-100" manufactured by Otsuka chemical Co., Ltd, "FP-100", "FP-110", "FP-300" and "FP-400" manufactured by Koka Co., Ltd, and "SPH-100" manufactured by Otsuka chemical Co., Ltd is preferable.

As the flame retardant other than the phosphazene compound, commercially available products such as "HCA-HQ" manufactured by Sanko corporation and "PX-200" manufactured by Daihachi chemical industries, Inc. can be used. As the flame retardant, those which are difficult to hydrolyze are preferred, and for example, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like are preferred.

From the viewpoint of remarkably obtaining the effect of the present invention, the content of the (I) flame retardant is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, and further more preferably 0.3 mass% or more, with 100 mass% of nonvolatile components in the resin composition. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less.

- (J) other additives

The resin composition may further contain other additives as optional components in addition to the above components. Examples of such additives include resin additives such as thickeners, defoaming agents, leveling agents, and adhesion imparting agents. These additives may be used alone or in combination of two or more. The respective contents can be appropriately set by those skilled in the art.

The method for producing the resin composition is not particularly limited, and examples thereof include: a method of adding a solvent or the like to the components to be mixed, if necessary, and mixing and dispersing the components using a rotary mixer or the like.

From the viewpoint of thinning of the printed wiring board and providing a cured product having excellent insulation properties even when the cured product of the resin composition is a thin film, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 70 μm or less, and still more preferably 60 μm or less and 50 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, and still more preferably 10 μm or more.

< other layer >

In one embodiment, the resin sheet may further include other layers as necessary. Examples of the other layer include a protective film provided on a surface of the resin composition layer not bonded to the support (i.e., a surface opposite to the support) and selected according to a substrate of the support. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion of dust or the like to the surface of the resin composition layer or generation of damage on the surface of the resin composition layer.

< method for producing resin sheet >

The resin sheet of the present invention can be produced, for example, by: a resin varnish in which a resin composition is dissolved in a solvent such as an organic solvent is prepared, and the resin varnish is applied to a support using a die coater or the like, and is dried so that the amount of the solvent contained in the resin composition layer becomes 5 mass% or less, thereby forming a resin composition layer.

The amount of the solvent contained in the resin composition layer is 5% by mass or less, preferably 3% by mass or less, more preferably 2.5% by mass or less. The lower limit is not particularly limited, and may be 0 mass% or more, 0.1 mass% or more, or the like.

The amount of the solvent (residual solvent amount) contained in the resin composition layer is determined by measuring the mass of the support, the initial mass of the resin sheet, and the dried mass of the resin sheet, and using the following formula;

the residual solvent amount (mass%) was 100 × (initial mass of resin sheet-dry mass of resin sheet)/(initial mass of resin sheet-mass of support).

Specifically, the support was cut into 10cm × 10cm, and the weight (mass) was measured with an electronic balance. The resin sheet in a state in which the support and the resin composition layer were laminated was cut into 10cm × 10cm, and the initial mass was measured using an electronic balance. Next, the resin sheet was placed on a metal mesh, heated in an oven set at 130 ℃ in advance for 15 minutes, transferred into a dryer, left to stand for 30 minutes, and cooled to room temperature. Then, the dry mass of the resin sheet was measured using an electronic balance. The mass of the support body, the initial mass of the resin sheet, and the mass of the resin sheet after drying, which were thus measured, were obtained by the above equations.

Examples of the organic solvent include: ketones such as acetone, Methyl Ethyl Ketone (MEK) and cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. One kind of the organic solvent may be used alone, or two or more kinds may be used in combination.

The drying can be carried out by a known method such as heating or hot air blowing. The drying conditions vary depending on the boiling point of the organic solvent in the resin varnish, and for example, in the case of using a resin varnish containing 30 to 60 mass% of an organic solvent, the resin composition layer having an amount of the solvent of 5 mass% or less can be formed by drying at 50 to 150 ℃ for 3 to 10 minutes. The average temperature for drying is preferably 91 ℃ or higher, more preferably 93 ℃ or higher, and still more preferably 95 ℃ or higher. The upper limit is not particularly limited, and may be 200 ℃ or lower, 150 ℃ or lower, or the like. The drying time is preferably 1 minute or more, more preferably 2 minutes or more, further preferably 3 minutes or more, preferably 10 minutes or less, further preferably 8 minutes or less, further preferably 7 minutes or less.

The resin sheet can be stored in a roll form. When the resin sheet has a protective film, the protective film can be peeled off and used.

< Properties and uses of resin sheet >

A cured product obtained by thermally curing the resin composition layer at 190 ℃ for 90 minutes has such a characteristic that the dielectric loss tangent is low. Therefore, the cured product brings about an insulating layer having a low dielectric loss tangent. The dielectric loss tangent is preferably less than 0.005, more preferably 0.0045 or less, still more preferably 0.003 or less. On the other hand, the lower limit of the dielectric loss tangent is not particularly limited, and may be 0.0001 or higher. The dielectric loss tangent can be measured by the method described in the examples below.

A cured product obtained by thermally curing the resin composition layer at 100 ℃ for 30 minutes and subsequently at 180 ℃ for 90 minutes has such a characteristic that the insulation reliability is excellent. Therefore, the cured product provides an insulating layer having excellent insulation reliability. As insulation reliability, in a HAST test of 300 hours at 130 ℃ and 85% RH, the insulation resistance value after the HAST test was more than 50% of the initial insulation resistance value before the HAST test. The insulation reliability can be evaluated by the method described in the examples described below.

A cured product obtained by thermally curing the resin composition layer at 190 ℃ for 90 minutes generally exhibits such a characteristic as excellent adhesion to a copper foil. Therefore, the cured product provides an insulating layer having excellent adhesion to the copper foil. The adhesion is preferably at least 0.5kgf/cm, more preferably at least 0.55kgf/cm, still more preferably at least 0.6 kgf/cm. On the other hand, the upper limit of the adhesiveness is not particularly limited, and may be 5kgf/cm or less. The adhesion can be measured by the method described in the examples described below.

The cured product obtained by heat-curing the resin composition layer at 190 ℃ for 90 minutes shows such a characteristic that the cured product has excellent adhesion to the copper foil after a HAST test for 100 hours under the conditions of 130 ℃ and 85% RH. Therefore, the cured product described above provides an insulating layer having excellent adhesion to a copper foil after the HAST test. The adhesion after HAST test is preferably at least 0.2kgf/cm, more preferably at least 0.35kgf/cm, still more preferably at least 0.4 kgf/cm. On the other hand, the upper limit of the adhesiveness after the HAST test is not particularly limited, and may be 5kgf/cm or less. The evaluation of the adhesion after the HAST test can be measured by the method described in the examples described below.

The resin sheet of the present invention can provide an insulating layer having excellent insulation reliability while reducing the dielectric loss tangent. Therefore, the resin sheet of the present invention can be preferably used as a resin sheet for insulation. Specifically, it can be preferably used as a resin sheet for forming an insulating layer (insulating layer forming resin sheet for forming a conductor layer) for forming a conductor layer (including a rewiring layer) formed on the insulating layer.

Further, it can be preferably used as: in a multilayer printed wiring board described later, a resin sheet for forming an insulating layer of the multilayer printed wiring board (resin sheet for forming an insulating layer of the multilayer printed wiring board) and a resin sheet for forming an interlayer insulating layer of the printed wiring board (resin sheet for forming an interlayer insulating layer of the printed wiring board) are used.

For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin sheet of the present invention can be preferably used as: a resin sheet for a rewiring-forming layer (a resin sheet for forming a rewiring-forming layer) as an insulating layer for forming a rewiring layer; and a resin sheet for sealing the semiconductor chip (resin sheet for sealing the semiconductor chip). At the time of manufacturing the semiconductor chip package, a rewiring layer may be further formed on the sealing layer;

(1) a step of laminating a temporary fixing film on the substrate,

(2) A step of temporarily fixing the semiconductor chip to the temporary fixing film,

(3) A step of forming a sealing layer on the semiconductor chip,

(4) A step of peeling the base material and the temporary fixing film from the semiconductor chip,

(5) A step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled, and

(6) and forming a rewiring layer as a conductor layer on the rewiring-forming layer.

The resin sheet of the present invention can provide an insulating layer having good component embeddability, and therefore, it can be preferably used even when the printed wiring board is a component-embedded circuit board.

[ printed Wiring Board ]

The printed wiring board of the present invention comprises an insulating layer formed from a cured product of the resin composition of the present invention.

The printed wiring board can be produced, for example, by a method including the steps (I), (II), and (III) in this order using the above-described resin sheet;

(I) laminating a resin sheet on the inner substrate so that the resin composition layer is bonded to the inner substrate,

(II) a step of forming an insulating layer by thermally curing the resin composition layer,

(III) a step of peeling off the support.

The "inner layer substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. The substrate may have a conductive layer on one surface or both surfaces thereof, and the conductive layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one surface or both surfaces of a substrate is sometimes referred to as an "inner layer circuit substrate". Further, an intermediate manufactured article in which an insulating layer and/or a conductor layer is to be further formed when manufacturing a printed wiring board is also included in the so-called "inner layer substrate" in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer substrate in which components are embedded may be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressure-bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for heat-pressure bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "heat-pressure bonding member") include a heated metal plate (SUS end plate or the like) and a metal roll (SUS roll). It is preferable that the heating and pressure-bonding member is not directly pressed against the resin sheet, but is pressed via an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

The lamination of the inner substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heating and press-bonding temperature is preferably in the range of 60 to 160 ℃, more preferably 80 to 140 ℃, the heating and press-bonding pressure is preferably in the range of 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the heating and press-bonding time is preferably in the range of 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably performed under reduced pressure of 26.7hPa or less.

The lamination can be carried out by means of a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Nikko Co., Ltd, a vacuum applicator (vacuum applicator) manufactured by Nikko-Materials, and a batch vacuum pressure laminator.

After the lamination, the heat-pressure bonded member is pressed from the support side under normal pressure (atmospheric pressure), for example, whereby the smoothing treatment of the laminated resin sheets can be performed. The pressing conditions for the smoothing treatment may be set to the same conditions as the above-described conditions for the heat and pressure bonding of the laminate. The smoothing treatment may be performed by a commercially available laminator. The lamination and smoothing treatment can be continuously performed using a commercially available vacuum laminator as described above.

In the step (II), the resin composition layer is thermally cured to form the insulating layer. The conditions for heat curing of the resin composition layer are not particularly limited, and the conditions generally employed in forming an insulating layer of a printed wiring board can be used.

For example, the heat curing conditions of the resin composition layer vary depending on the kind of the resin composition, and the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, and still more preferably 170 to 210 ℃. The curing time may be preferably from 5 minutes to 120 minutes, more preferably from 10 minutes to 100 minutes, and still more preferably from 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 is preheated at a temperature of 50 ℃ or higher and lower than 120 ℃ (preferably 60 ℃ or higher and 115 ℃ or lower, more preferably 70 ℃ or higher and 110 ℃ or lower) for 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, further preferably 15 minutes to 100 minutes) before the resin composition layer is thermally cured.

The insulating layer is formed by using a cured product of the resin composition of the present invention, and therefore, the thickness of the insulating layer can be reduced. The thickness of the insulating layer is preferably 30 μm or less, more preferably 20 μm or less, further preferably 15 μm or less and 10 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be usually 1 μm or more and 5 μm or more.

After the completion of step (II), the support is peeled in step (III) from the viewpoint of obtaining an insulating layer which can reduce the dielectric loss tangent and has excellent insulation reliability.

In the production of the printed wiring board, (IV) a step of forming a hole in the insulating layer, (V) a step of roughening the insulating layer, and (VI) a step of forming a conductor layer may be further performed. These steps (IV) to (VI) can be carried out by various methods known to those skilled in the art used for the production of printed wiring boards. The steps (IV) to (V) may be performed before or after the step (III). Usually, the step (IV) is performed after the step (III). The formation of the insulating layer and the conductive layer in the steps (II) to (V) may be repeated as necessary to form a multilayer wiring board.

In the step (IV), a hole is formed in the insulating layer, whereby a hole such as a through hole or a via hole can be formed in the insulating layer. The step (IV) can be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition for forming the insulating layer. The size and shape of the hole may be determined as appropriate according to the design of the printed wiring board.

The step (V) is a step of roughening the insulating layer. In general, in this step (V), stain (scum) is also removed. The roughening treatment step and conditions are not particularly limited, and known steps and conditions generally used for forming an insulating layer of a printed wiring board can be used. For example, the insulating layer is subjected to a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order. The swelling solution used in the roughening treatment is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, and an alkali solution is preferred, and a sodium hydroxide solution and a potassium hydroxide solution are more preferred. Examples of commercially available Swelling liquids include "spinning Dip securidh P (スウェリング, ディップ, セキュリガンス P)", "spinning Dip securidh SBU (スウェリング, ディップ, セキュリガンス SBU)", and "spinning Dip securidh P (スウェリングディップ, セキュリガント P)" manufactured by atmott JAPAN (ato ech JAPAN). The swelling treatment using the swelling solution is not particularly limited, and for example, the swelling treatment can be performed by immersing the insulating layer in the swelling solution at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of controlling the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40 to 80 ℃ for 5 to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganic acid solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing solution securiganteh P" manufactured by amett japan. The neutralizing solution used for the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction solution securiganteh P" manufactured by amatt japan. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ℃ for 1 to 30 minutes. From the viewpoint of handling and the like, it is preferable to dip the object subjected to the roughening treatment with the oxidizing agent in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.

In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 300nm or less, more preferably 250nm or less, and still more preferably 200nm or less. The lower limit is not particularly limited, but is preferably 30nm or more, more preferably 40nm or more, and still more preferably 50nm or more. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Step (VI) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains 1 or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include layers formed of an alloy of 2 or more metals selected from the above metals (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoint of versatility of forming a conductor layer, cost, easiness of pattern formation, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a single metal layer of copper is even more preferable.

The conductor layer may have a single-layer structure, or may have a multilayer structure in which 2 or more layers of single metal layers or alloy layers made of different metals or alloys are stacked. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer may be formed by plating. For example, the conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method, and is preferably formed by the semi-additive method from the viewpoint of ease of manufacturing. An example of forming a conductor layer by a semi-additive method is shown below.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer in accordance with a desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, unnecessary plating seed layers are removed by etching or the like, whereby a conductor layer having a desired wiring pattern can be formed.

[ semiconductor device ]

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

Examples of the semiconductor device include various semiconductor devices used in electric products (for example, a computer, a mobile phone, a digital camera, a television, and the like) and vehicles (for example, a motorcycle, an automobile, a train, a ship, an aircraft, and the like).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at a conducting position of a printed wiring board. The "conduction position" refers to a "position of a printed wiring board at which an electrical signal is conducted", and the position thereof may be any of a surface or a buried position. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

A method of mounting a semiconductor chip in the manufacture of a semiconductor device is not particularly limited as long as the semiconductor chip can function effectively, and specific examples thereof include a wire bonding mounting method, a flip chip mounting method, a mounting method using a Build-Up Layer without solder (BBUL), a mounting method using an Anisotropic Conductive Film (ACF), and a mounting method using a non-conductive film (NCF). The "mounting method by a build-up solderless layer (BBUL)" referred to herein is a "mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip is connected to a wiring on the printed wiring board".

Examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "part" and "%" mean "part by mass" and "% by mass", respectively, unless otherwise stated. Unless otherwise specified, the reaction is carried out at normal temperature and atmospheric pressure.

< determination of oxygen permeability >

The oxygen permeability of the support was measured in accordance with JIS K7126 (isobaric method) at 23 ℃ and 50% RH using an oxygen permeability measuring apparatus (OX-TRAN 2/21, manufactured by MOCON).

< determination of Water vapor Transmission Rate >

The water vapor transmission rate of the support was measured in an atmosphere of 40 ℃ and 90% RH according to JIS K7129 using a water vapor transmission rate measuring apparatus (manufactured by MOCON, Inc., PERMATRAN-W3/34).

Method for determining weight loss rate at < 200 ℃ >

The weight loss at 200 ℃ was measured using "TG/DTA EXSTAR 6300" manufactured by Hitachi High-Tech Science. Specifically, about 10mg of an epoxy resin was weighed in an aluminum sample pan, and the weight of the sample at each temperature was measured by heating the epoxy resin from 30 ℃ to 550 ℃ at a heating rate of 10 ℃/min in an atmosphere of 200 mL/min air flow in an open state without being covered. From the obtained results, the weight loss ratio at 200 ℃ was calculated using the following formula: weight loss ratio (mass%) at 200 ℃ was 100 × (mass before heating-mass at 200 ℃)/mass before heating.

< method for measuring amount of solvent contained in resin composition layer >

(1) Mass measurement of support

The support was cut into 10cm × 10cm, and the weight was measured using an electronic balance. The measurement was performed for 3 samples, and the average value thereof was taken as the mass of the support.

(2) Measurement of quality of resin sheet

The resin sheet in a state in which the support and the resin composition layer were laminated was cut into 10cm × 10cm, and the initial mass was measured using an electronic balance. Next, the resin sheet was placed on a metal mesh, heated in an oven set at 130 ℃ in advance for 15 minutes, transferred into a dryer, left to stand for 30 minutes, and cooled to room temperature. Then, the dry mass of the resin sheet was measured using an electronic balance. The initial mass and the dry mass were measured for each of the 3 samples, and the amount of the solvent (amount of residual solvent) contained in the resin composition layer was calculated using the following formula using the average value thereof:

< preparation of resin composition 1 >

10 parts of a bisphenol A-type epoxy resin ("828 EL" manufactured by Mitsubishi chemical corporation, having an epoxy equivalent of about 180g/eq.)10 parts, a bisphenol AF-type epoxy resin ("YX 7760" manufactured by Mitsubishi chemical corporation, having an epoxy equivalent of about 238g/eq.), 20 parts of a biphenyl-type epoxy resin ("NC-3000-L" manufactured by Nippon chemical corporation, having an epoxy equivalent of about 269g/eq.)25 parts, 7 parts of a liquid 1, 4-glycidylcyclohexane-type epoxy resin ("ZX 1658 GS" manufactured by Nippon iron chemical corporation, having an epoxy equivalent of about 135g/eq., having a weight loss rate of 7.2% at 200 ℃ in a TG-DTA device measurement, 3 parts of a phosphazene resin ("SPS-100" manufactured by Datsubishi chemical corporation), and 10 parts of a phenoxy resin ("YX 7553BH 30" manufactured by Mitsubishi chemical corporation, a solution of 30% by mass of MEK and cyclohexanone) were mixed with 20 parts of 20 parts while stirring, 40 parts of solvent naphtha are heated and dissolved. After cooling to room temperature, 86 parts of an active ester type curing agent ("EXB 9416-70 BK" manufactured by DIC, a solution of methyl isobutyl ketone having a nonvolatile content of about 330g/eq in terms of active group equivalent) 10 parts of a phenol type curing agent ("LA 3018-50P" manufactured by DIC, a solution of 2-methoxypropanol having a solid content of 50% in terms of active group equivalent of about 151 g/eq.), 2 parts of a naphthol type curing agent ("SN 395" manufactured by Nisshinoki chemical, a solution of about 107g/eq in terms of active group equivalent), and a carbodiimide type curing agent ("V-03 ″, active group equivalent of about 216g/eq., solid content of 50 mass% in toluene solution) 10 parts, curing accelerator (4-Dimethylaminopyridine (DMAP), solid content of 5 mass% in MEK solution) 8 parts, and spherical silica (average particle diameter 0.5 μm, specific surface area 5.8 m) surface-treated with a phenylaminosilane coupling agent (KBM 573, manufactured by shin-Etsu chemical Co., Ltd.)²(g, product of Yadmama, SO-C2), 400 parts, uniformly dispersed in a high-speed rotary mixer, and filtered through a drum filter (product of ROKITECHNO, SHP 100), to give resin composition 1.

< preparation of resin composition 2 >

In the production of the resin composition 1,

1) the amount of biphenyl type epoxy resin ("NC-3000-L" manufactured by Nippon chemical Co., Ltd., epoxy equivalent of about 269g/eq.) was changed from 25 parts to 20 parts,

2) 7 parts of a liquid 1, 4-glycidylcyclohexane-type epoxy resin ("ZX 1658 GS" manufactured by Nippon iron chemical Co., Ltd., an epoxy equivalent of about 135g/eq., and a weight loss ratio at 200 ℃ of 7.2% in the measurement using a TG-DTA apparatus) as a volatile epoxy resin was changed to 12 parts of a (meth) acrylic ester ("NK ester A-DOG" manufactured by Newzhongcun chemical industry Co., Ltd., molecular weight 326) as a radical polymerizable resin,

3) 0.2 part of a polymerization initiator (PERBUTYLC, manufactured by Nichikoku corporation) was further used;

in addition to the above, resin composition 2 was produced in the same manner as resin composition 1.

< preparation of resin composition 3 >

In the production of the resin composition 1,

1) the amount of biphenyl type epoxy resin ("NC-3000-L" manufactured by Nippon chemical Co., Ltd., epoxy equivalent of about 269g/eq.) was changed from 25 parts to 10 parts,

2) 10 parts of a modified naphthalene type epoxy resin ("ESN-475V" manufactured by Nichika chemical Co., Ltd., epoxy equivalent of about 330g/eq.) was used,

3) 5 parts of (meth) acrylic ester (NK ester A-DOG, molecular weight 326, available from Xinzhongcun chemical industries, Ltd.) as a radical polymerizable resin was used,

4) 0.2 part of a polymerization initiator ("PERBUTYLC" manufactured by Nichikoku Co., Ltd.) was used;

in addition to the above, a resin composition 3 was produced in the same manner as the production of the resin composition 1.

< preparation of resin composition 4 >

10 parts of bisphenol AF-type epoxy resin ("YX 7760" manufactured by Mitsubishi chemical corporation, epoxy equivalent of about 238), 20 parts of biphenyl-type epoxy resin ("NC-3000-L" manufactured by Nippon chemical corporation, epoxy equivalent of about 269g/eq.)10 parts of modified naphthalene-type epoxy resin ("ESN-475V" manufactured by Nippon chemical corporation, epoxy equivalent of about 330g/eq.)20 parts of bicresol-type epoxy resin ("YX 4000H" manufactured by Mitsubishi chemical corporation, epoxy equivalent of about 190g/eq.)7 parts of naphthalene-type tetrafunctional epoxy resin ("HP-4710" manufactured by DIC corporation, epoxy equivalent of about 170g/eq.)3 parts of liquid 1, 4-glycidylcyclohexane-type epoxy resin ("ZX 1658 GS" manufactured by Nippon chemical corporation, epoxy equivalent of about 135 g/eq.) as a volatile epoxy resin, and 7.2% weight loss at 200 ℃ in TG-DTA apparatus were measured with stirring, 10 parts of a phenoxy resin (a 1: 1 solution of MEK and cyclohexanone having a solid content of 30% by mass, manufactured by Mitsubishi chemical corporation, YX7553BH 30) were dissolved in 20 parts of MEK and 40 parts of solvent naphtha by heating. After cooling to room temperature, 5 parts of (meth) acrylic ester (NK ester A-DOG, molecular weight 326, manufactured by Ningmura chemical industries, Ltd.), 94 parts of an active ester curing agent (65% by mass of a toluene solution having a nonvolatile content and an active group equivalent of about 223g/eq. "HPC 8000-65T", manufactured by DIC Co., Ltd.), 5 parts of a phenol curing agent (50% by mass of a 2-methoxypropanol solution having an active group equivalent of about 151g/eq., and a solid content of 50%) 3 parts of a benzoxazine curing agent (MEK solution having a solid content of 50% by mass and a benzoxazine ring equivalent of about 218g/eq. "manufactured by JFE chemical Co., Ltd.), a carbodiimide curing agent (V-03, manufactured by Nisshinbo chemical Co., Ltd.," an active group equivalent of about 216 g/eq.), toluene solution having a solid content of 50 mass%), 4 parts of a methyl ethyl ketone solution having a solid content of 10 mass% of a curing accelerator 1-benzyl-2-phenylimidazole (1B 2PZ, manufactured by Shikoku chemical industries Co., Ltd.), and a polymerization initiator (PER, manufactured by Nikkiso Co., Ltd.) (BUTYL C') 0.2 parts, 2 parts of rubber particles (AICA INDUSTRIAL CORE. "IM 401-4-14", core-shell rubber particles having a core of polybutadiene and a shell of a copolymer of styrene and divinylbenzene), 3 parts of a flame retardant (SAIGAIL CORE. "HCA-HQ-HST", 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide having an average particle diameter of 1.5 μm) and spherical silica (average particle diameter 0.5 μm, specific surface area 5.8m, KBM573 ") surface-treated with a phenylaminosilane coupling agent (shin-Etsu. Chemie., Inc.")²(g, product of Yadmama corporation, "SO-C2"), 400 parts by weight, uniformly dispersed in a high-speed rotary mixer, and then filtered through a drum filter (product of ROKITECHNO, "SHP 100"), to prepare a resin composition 4.

< preparation of resin composition 5 >

In the preparation of the resin composition 1, 7 parts of a liquid 1, 4-glycidylcyclohexane-type epoxy resin (ZX 1658GS, manufactured by Nippon iron Chemicals, Inc., having an epoxy equivalent of about 135g/eq., and a weight loss rate of 7.2% at 200 ℃ in a measurement using a TG-DTA apparatus) as a volatile epoxy resin was changed to 7 parts of a liquid diglycidyl ether phthalate-type epoxy resin (EX-721, manufactured by Nagase ChemteX, Inc., having an epoxy equivalent of about 154g/eq., and a weight loss rate of 4.2% at 200 ℃ in a measurement using a TG-DTA apparatus) as a volatile epoxy resin;

in addition to the above, resin composition 5 was produced in the same manner as resin composition 1.

< resin composition 6 >

Resin composition 6 was produced in the same manner as resin composition 2 except that 12 parts of (meth) acrylate (NK ester a-DOG, molecular weight 326, manufactured by shin-mura chemical industries, ltd.) as a radical polymerizable resin was changed to 20 parts of a styrene-modified polyphenylene ether resin (a toluene solution having a nonvolatile content of 60 mass% and a number average molecular weight of 1200, manufactured by mitsubishi gas chemical corporation, ltd.) as a radical polymerizable resin in resin composition 2.

The components used in the resin compositions 1 to 6 and their amounts are shown in the following tables;

[ Table 1]

(Table 1)

。

< example 1 >

A support 1 (a support (total thickness: 53 μm, oxygen permeability: 0.1 cc/m) obtained by applying the resin composition 1 to a support 1 (a PET film having a thickness of 12 μm and formed with a silica vapor-deposited layer of 300nm and bonded to one surface of a PET film having a thickness of 38 μm by an alkyd resin-based release treatment using a die coater and to the other surface thereof via an adhesive layer having a thickness of 3 μm) was coated with the resin composition 1 by a die coater²Day, water vapor transmission rate 1.2g/m²Day)) so that the thickness of the resin composition after drying became 40 μm, and dried at 80 to 120 ℃ (average 100 ℃) for 6 minutes. The amount of the solvent contained in the resin composition layer at this time was 2.5 mass%. Then, a polypropylene film having a thickness of 15 μm was laminated on the surface of the resin composition layer, and the film was wound into a roll. The rolled resin sheet was cut into a width of 507mm, thereby obtaining a sheet-like resin sheet 1 having dimensions of 507mm × 336 mm.

< example 2 >

In example 1, resin composition 1 was changed to resin composition 2. In the same manner as in example 1 except for the above, a resin sheet 2 was obtained. The amount of the solvent contained in the resin composition layer was 2.6 mass%.

< example 3 >

In example 1, resin composition 1 was changed to resin composition 3. In the same manner as in example 1 except for the above, a resin sheet 3 was obtained. The amount of the solvent contained in the resin composition layer was 2.5 mass%.

< example 4 >

In example 1, resin composition 1 was changed to resin composition 4. In the same manner as in example 1 except for the above, a resin sheet 4 was obtained. The amount of the solvent contained in the resin composition layer was 2.3 mass%.

< example 5 >

In example 1, resin composition 1 was changed to resin composition 5. In the same manner as in example 1 except for the above, a resin sheet 5 was obtained. The amount of the solvent contained in the resin composition layer was 2.5 mass%.

< example 6 >

In example 1, resin composition 1 was changed to resin composition 6. In the same manner as in example 1 except for the above, a resin sheet 6 was obtained. The amount of the solvent contained in the resin composition layer was 2.7 mass%.

< example 7 >

In example 1, a support 1 (a support (total thickness: 53 μm, oxygen permeability: 0.1 cc/m) obtained by applying an alkyd resin-based release treatment to one surface of a 38 μm thick PET film and bonding a 12 μm thick PET film having a 300nm silica vapor deposition layer formed thereon to the other surface via a3 μm thick adhesive layer was used²Day, water vapor transmission rate 1.2g/m²Day)) was changed to a support 2 (a support (total thickness: 40 μm, oxygen permeability: 0.1 cc/m) obtained by applying an alkyd resin-based mold release treatment to one surface of a 38 μm thick PET film and applying an organic barrier layer (polyvinyl alcohol) having a thickness of 2 μm to the other surface²Day, water vapor transmission rate 12g/m²Day)). In the same manner as in example 1 except for the above, a resin sheet 7 was obtained. The amount of the solvent contained in the resin composition layer was 2.5 mass%.

< example 8 >

In example 1, a support 1 (a support (total thickness: 53 μm, oxygen permeability: 0.1 cc/m) obtained by applying an alkyd resin-based release treatment to one surface of a 38 μm thick PET film and bonding a 12 μm thick PET film having a 300nm silica vapor deposition layer formed thereon to the other surface via a3 μm thick adhesive layer was used²Day, water vapor transmission rate 1.2g/m²Day)) was changed to a support 3 (a support (total thickness: 40 μm, oxygen permeability: 0.1 cc/m) obtained by applying an organic barrier layer (ethylene-vinyl alcohol copolymer) having a thickness of 2 μm to one surface of a 38 μm PET film and then applying an alkyd resin-based mold release treatment to the other surface²Day, water vapor transmission rate 11g/m²Day)). In addition to the above, the same operation as in example 1 was carried out,a resin sheet 8 was obtained. The solvent amount of the solvent contained in the resin composition layer was 2.5 mass%.

< example 9 >

In example 1, a support 1 (a support (total thickness: 53 μm, oxygen permeability: 0.1 cc/m) obtained by applying an alkyd resin-based release treatment to one surface of a 38 μm thick PET film and bonding a 12 μm thick PET film having a 300nm silica vapor deposition layer formed thereon to the other surface via a3 μm thick adhesive layer was used²Day, water vapor transmission rate 1.2g/m²Day)) was changed to a support 4 (a support (total thickness: 40 μm, oxygen permeability: 0.1 cc/m) obtained by applying an alkyd resin-based mold release treatment to one surface of a 38 μm thick PET film and coating an organic barrier layer (polyvinylidene chloride) having a thickness of 2 μm to the other surface²Day, water vapor transmission rate 5.0g/m²Day)). In the same manner as in example 1 except for the above, a resin sheet 9 was obtained. The solvent amount of the solvent contained in the resin composition layer was 2.5 mass%.

< example 10 >

In example 1, a support 1 (a support (total thickness: 53 μm, oxygen permeability: 0.1 cc/m) obtained by applying an alkyd resin-based release treatment to one surface of a 38 μm thick PET film and bonding a 12 μm thick PET film having a 300nm silica vapor deposition layer formed thereon to the other surface via a3 μm thick adhesive layer was used²Day, water vapor transmission rate 1.2g/m²Day)) was changed to the support 5 (support obtained by subjecting one surface of a PEN film 25 μm in thickness to alkyd resin-based release treatment (total thickness 25 μm, oxygen permeability 14 cc/m)²Day, water vapor transmission rate 5.6g/m²Day)). In the same manner as in example 1 except for the above, a resin sheet 10 was obtained. The solvent amount of the solvent contained in the resin composition layer was 2.5 mass%.

< example 11 >

In example 1, a support 1 (a support obtained by applying alkyd-based release treatment to one surface of a 38 μm thick PET film and bonding a 12 μm thick PET film having a 300nm silica vapor-deposited layer formed thereon to the other surface thereof via a3 μm thick adhesive layer) (total thickness: 53 μm,oxygen permeability of 0.1cc/m²Day, water vapor transmission rate 1.2g/m²Day)) was changed to a support 6 (support subjected to alkyd resin-based mold release treatment on one surface of a PEN film having a thickness of 38 μm (total thickness 38 μm, oxygen permeability 10 cc/m)²Day, water vapor transmission rate 3.8g/m²Day)). In the same manner as in example 1 except for the above, a resin sheet 11 was obtained. The solvent amount of the solvent contained in the resin composition layer was 2.5 mass%.

< example 12 >

In example 1, a support 1 (a support (total thickness: 53 μm, oxygen permeability: 0.1 cc/m) obtained by applying an alkyd resin-based release treatment to one surface of a 38 μm thick PET film and bonding a 12 μm thick PET film having a 300nm silica vapor deposition layer formed thereon to the other surface via a3 μm thick adhesive layer was used²Day, water vapor transmission rate 1.2g/m²Day)) was changed to a support 7 (a support obtained by subjecting the PET surface side of the metal film-attached film described in example 1 of Japanese patent No. 5500074 to an alkyd resin-based mold release treatment (total thickness: 41 μm, oxygen permeability: 0.1 cc/m)²Day, water vapor transmission rate 0.5g/m²Day)). In the same manner as in example 1 except for the above, a resin sheet 12 was obtained. The solvent amount of the solvent contained in the resin composition layer was 2.5 mass%.

< example 13 >

In example 1, a support 1 (a support (total thickness: 53 μm, oxygen permeability: 0.1 cc/m) obtained by applying an alkyd resin-based release treatment to one surface of a 38 μm thick PET film and bonding a 12 μm thick PET film having a 300nm silica vapor deposition layer formed thereon to the other surface via a3 μm thick adhesive layer was used²Day, water vapor transmission rate 1.2g/m²Day)) was changed to a support 8 (a support obtained by subjecting one side of the metal film-attached film described in example 1 of Japanese patent No. 5500074 to an alkyd resin-based mold release treatment (total thickness: 41 μm, oxygen permeability: 0.1 cc/m)²Day, water vapor transmission rate 0.5g/m²Day)). In the same manner as in example 1 except for the above, a resin sheet 13 was obtained. Solution contained in resin composition layerThe solvent amount of the agent was 2.5 mass%.

< example 14 >

In example 1, a support 1 (a support (total thickness: 53 μm, oxygen permeability: 0.1 cc/m) obtained by applying an alkyd resin-based release treatment to one surface of a 38 μm thick PET film and bonding a 12 μm thick PET film having a 300nm silica vapor deposition layer formed thereon to the other surface via a3 μm thick adhesive layer was used²Day, water vapor transmission rate 1.2g/m²Day)) was changed to a support 9 (total thickness 18 μm, oxygen permeability 0.1cc/m²Day, water vapor transmission rate 0.1g/m²Day)). In the same manner as in example 1 except for the above, a resin sheet 14 was obtained. The solvent amount of the solvent contained in the resin composition layer was 2.5 mass%.

< comparative example 1 >

In example 1, a support 1 (a support (total thickness: 53 μm, oxygen permeability: 0.1 cc/m) obtained by applying an alkyd resin-based release treatment to one surface of a 38 μm thick PET film and bonding a 12 μm thick PET film having a 300nm silica vapor deposition layer formed thereon to the other surface via a3 μm thick adhesive layer was used²Day, water vapor transmission rate 1.2g/m²Day)) was changed to the support 10 (alkyd resin-based release-treated PET film (thickness 38 μm, oxygen permeability 40 cc/m)²Day, water vapor transmission rate 15g/m²Day). In the same manner as in example 1 except for the above, a resin sheet 15 was obtained. The solvent amount of the solvent contained in the resin composition layer was 2.5 mass%.

< comparative example 2 >

In comparative example 1, resin composition 1 was changed to resin composition 2. In the same manner as in comparative example 1 except for the above, a resin sheet 16 was obtained. The solvent amount of the solvent contained in the resin composition layer was 2.6 mass%.

< comparative example 3 >

In example 1, the resin composition 1 was changed to the resin composition 3, and the drying conditions were changed from 6 minutes at 80 ℃ to 120 ℃ (average 100 ℃) to 4 minutes at 80 ℃ to 100 ℃ (average 90 ℃). In the same manner as in example 1 except for the above, a resin sheet 17 was obtained. The solvent amount of the solvent contained in the resin composition layer was 5.1 mass%.

< measurement of copper foil adhesion >

(1) Preparation of samples

A glossy surface of an electrolytic copper foil ("3 EC-III" manufactured by mitsui metals mining, thickness 35 μm) was immersed in a microetching solution ("CZ-8101" manufactured by MEC), a roughening treatment (Ra value of 1 μm) was performed on the copper surface, and then an anticorrosive treatment was performed using an anticorrosive solution ("CL 8300" manufactured by MEC). The obtained copper foil is referred to as a CZ copper foil. Further, the heat treatment was carried out in an oven at 130 ℃ for 30 minutes.

As the inner layer circuit board, a glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil 18 μm thick, substrate 0.4mm thick, "R1515A" manufactured by Sonar corporation) on which an inner layer circuit was formed was prepared. Then, using a batch vacuum pressure laminator ("MVLP-500" manufactured by ltd., ltd.) the resin sheets 1 to 17 were laminated on both surfaces of the inner layer circuit board so that the resin composition layer was bonded to the inner layer circuit board. The lamination was carried out by: the pressure was reduced for 30 seconds to 13hPa or less, and then pressure-bonded at 100 ℃ under a pressure of 0.74MPa for 30 seconds. After lamination, the support is peeled off. The treated surface of the CZ copper foil was laminated on the exposed resin composition layer under the same conditions as described above. Then, the resin composition layer was cured at 190 ℃ for 90 minutes to form an insulating layer, thereby producing a sample having a structure of CZ copper foil/insulating layer/inner circuit board/insulating layer/CZ copper foil.

(2) Measurement of copper foil adhesion (adhesion 1) before high temperature and high humidity environment test (HAST) the prepared sample was cut into 150 × 30mm pieces. A cut of a portion having a width of 10mm and a length of 100mm was cut out from a copper foil portion of a small piece by using a cutter, one end of the copper foil in the longitudinal direction was peeled off and held by a jig ("AC-50C-SL" manufactured by TSE company), and the load when the piece was peeled off at a speed of 50 mm/min in the vertical direction by using an Instron universal tester according to JIS C6481 was measured at room temperature. The load thus measured is referred to as "adhesion 1".

(3) Measurement of copper foil adhesion (adhesion 2) after high temperature and high humidity environment test (HAST) the prepared sample was cut into 150 × 30mm pieces. A cut mark of a portion having a width of 10mm and a length of 100mm was cut out from a copper foil portion of the small piece by using a cutter, and a high-temperature high-humidity environment test was performed for 100 hours under conditions of 130 ℃ and 85% RH by using a high accelerated life test apparatus ("PM 422" manufactured by NAKAI CHEMICAL Co., Ltd.). Then, one end of the copper foil in the longitudinal direction was peeled off and held by a jig ("AC-50C-SL" manufactured by TSE), and the load at which the copper foil was peeled off at a speed of 50 mm/min at a vertical direction of 35mm was measured at room temperature according to JIS C6481 using an Instron universal tester. The load thus measured is referred to as "adhesion 2". The adhesion 2 was evaluated according to the following criteria:

very good: 0.4kgf/cm or more and no bulge

Good: 0.2kgf/cm or more and less than 0.4kgf/cm and no bulge

X: less than 0.2kgf/cm, or 0.2kgf/cm or more but has a bulge.

< determination of dielectric loss tangent >

(1) Production of cured product for evaluation

The polypropylene films having a thickness of 15 μm were peeled from the resin sheets 1 to 17, and the supports used in the examples and comparative examples were laminated so that the release surfaces thereof were in contact with the resin compositions. The lamination was carried out by: the pressure was reduced for 30 seconds to 13hPa or less, and then pressure-bonded at 100 ℃ under a pressure of 0.74MPa for 30 seconds. After the lamination, the resin composition layer was put into an oven at 190 ℃ and then thermally cured under curing conditions of 90 minutes. After the thermosetting, the support bodies on both sides of the resin composition layer were peeled off to obtain a sheet-like cured product. The resulting cured product was referred to as "cured product for evaluation".

(2) Determination of dielectric loss tangent

The cured product for evaluation was cut into a length of 80mm and a width of 2mm to obtain an evaluation sample. For the evaluation sample, the dielectric loss tangent was measured by the resonance cavity perturbation method at a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃ using "HP 8362B" manufactured by Agilent Technologies. The 2 evaluation samples were measured, and the average value was calculated. The average value of the obtained dielectric loss tangent was evaluated according to the following criteria:

very good: 0.0030 or less

Good: more than 0.0030 and less than 0.0050

X: 0.0050 or more.

< evaluation of insulation reliability >

(1) Production of laminate for evaluation

An imide film having a comb-shaped electrode (line width/pitch 15 μm/15 μm) was prepared. The resin sheets 1 to 17 are laminated by using a batch vacuum pressure laminator ("MVLP-500" manufactured by co-Ltd.) so that the resin composition layer is bonded to the circuit forming surface of the imide film. The lamination was carried out by: the pressure was reduced for 30 seconds to 13hPa or less, and then pressure-bonded at 100 ℃ under a pressure of 0.74MPa for 30 seconds. Then, the laminate for evaluation was obtained by performing a heat treatment at 100 ℃ for 30 minutes, followed by a heat treatment at 180 ℃ for 90 minutes.

(2) Evaluation of insulation reliability

After measuring the initial insulation resistance value of the laminate for evaluation obtained, the laminate was placed in a high-temperature and high-humidity chamber at 130 ℃ and a humidity of 85%, a voltage of 3.3V was applied, and a HAST test was performed in the chamber at 130 ℃ and 85% RH for 300 hours. The insulation resistance value of the laminate for evaluation after the lapse of 300 hours was measured and evaluated according to the following criteria:

good: the insulation resistance value after 300 hours exceeds 50% of the initial insulation resistance value;

x: the insulation resistance value after the lapse of 300 hours is 50% or less of the initial insulation resistance value.

[ Table 2]

(Table 2)

[ Table 3]

(Table 3)

。

In comparative example 3, the measurements of adhesion 1 and adhesion 2 were carried out, but it was confirmed that swelling occurred at the interface between the insulating layer and the CZ copper foil.

It was confirmed that, in each example, even when the components (A-2), (C) to (I) were not contained, the results were similar to those in the above examples, although the differences were different in degree.

Claims

1. A resin sheet comprising a support and, provided on the support, a resin composition layer comprising a resin composition,

wherein the oxygen permeability of the support measured by the method according to JIS K7126 is 20cc/m in an atmosphere of 23 ℃ and 50% RH²As well as below the seed and seed stage,

the resin composition contains any of (A-1) a volatile epoxy resin and (B) a radical polymerizable resin.

2. The resin sheet according to claim 1, wherein the water vapor transmission rate of the support measured by a method according to JIS K7129 is 20g/m in an atmosphere of 40 ℃ and 90% RH²And seed and root.

3. The resin sheet according to claim 1, wherein the total content of the component (A-1) and the component (B) is 1% by mass or more and 20% by mass or less, assuming that the resin component is 100% by mass.

4. The resin sheet according to claim 1, wherein the total content of the component (A-1), the component (B) and the solvent is 1 to 20% by mass, based on 100% by mass of the resin component.

5. The resin sheet according to claim 1, wherein the resin composition further contains (C) an inorganic filler.

6. The resin sheet according to claim 5, wherein the content of the component (C) is 50% by mass or more, assuming that the nonvolatile content of the resin composition is 100% by mass.

7. A printed wiring board comprising an insulating layer formed by using a cured product of a resin composition layer of the resin sheet according to any one of claims 1 to 6.

8. A semiconductor device comprising the printed wiring board of claim 7.

9. A method of manufacturing a printed wiring board, the method comprising in order:

(I) laminating the resin sheet according to any one of claims 1 to 6 on an inner layer substrate so that the resin composition layer is bonded to the inner layer substrate;

(II) forming an insulating layer by thermally curing the resin composition layer; and

(III) a step of peeling off the support.