Resin composition, resin film, circuit board and semiconductor wafer packaging

Abstract

[The technical problem to be solved] A resin composition is provided that can produce an insulating layer with excellent thermal conductivity and excellent peel strength to metal layers, a resin film using the resin composition, a circuit board, and a semiconductor wafer package. Technical means to solve the problem A resin composition comprising (A) a polymer compound having one or more structures selected from polybutadiene, polysiloxane, poly(meth)acrylate, polyalkylene, polyalkylene oxide, polyisoprene, polyisobutylene, and polycarbonate, (B) an epoxy resin, (C) a thermally conductive filler, and (D) an active ester curing agent.

Description

Technical Field

[0001] The present invention relates to a resin composition, and also to a resin sheet, a circuit substrate, and a semiconductor chip package using the resin composition. Prior Art

[0002] In recent years, with the miniaturization and increased functionality of electronic devices, the density of semiconductor components mounted on printed wiring boards has tended to increase. This increased functionality of mounted semiconductor components has also led to a demand for technologies that can efficiently dissipate the heat generated by these components. When curing a resin composition containing a thermally conductive filler to form an insulating layer, increasing the content of the thermally conductive filler in the resin composition can improve the thermal conductivity of the resulting insulating layer. However, increasing the content of the thermally conductive filler to achieve sufficient thermal conductivity tends to deteriorate the adhesion strength of the resulting insulating layer to the metal layer on which the wiring is to be formed.

[0003] For example, Patent Document 1 discloses that when a printed wiring board is formed by curing a resin composition containing aluminum nitride or silicon nitride to form an insulating layer, the insulating layer not only exhibits thermal diffusivity but also exhibits excellent adhesion strength (peel strength) with a conductor layer having a low surface roughness, thereby effectively diffusing heat. [Prior Art Literature] [Patent Document]

[0004] [Patent Document 1] International Publication No. 2014 / 208352 Summary of the Invention

[0005] [Problems to be solved by the invention]

[0006] In recent years, with the miniaturization and increased functionality of electronic devices, the trend toward thinner and caseless substrates has necessitated the search for materials that, in addition to thermal diffusivity and adhesion (peel strength), can also suppress warping during the formation of insulating layers. These properties present a trade-off, making the design of a resin that strikes a balance extremely difficult.

[0007] The present invention is proposed to solve the above-mentioned problems and provides a resin composition capable of producing a cured product that has a good balance between excellent thermal conductivity, excellent peel strength against metal layers, and suppressing the amount of warpage generated during the formation of an insulating layer; and a resin sheet, a circuit substrate, and a semiconductor chip package using the resin composition. [Solution to the problem]

[0008] The present inventors have discovered that a composition containing: (A) a polymer compound having one or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkylene oxide structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure; (B) an epoxy resin; (C) a thermally conductive filler; and (D) an active ester hardener can produce an insulating layer having excellent thermal conductivity, excellent peel strength with respect to a metal layer (particularly a metal layer formed by plating), and an excellent effect in suppressing warpage during the formation of the insulating layer. This discovery has led to the completion of the present invention.

[0009] That is, the present invention includes the following contents. [1] A resin composition comprising: (A) a polymer compound having one or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkylene oxide structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in its molecule; (B) Epoxy resin, (C) thermally conductive fillers, and (D) Active ester hardener. [2] The resin composition as described in [1], wherein the peel strength between the cured product formed by thermally curing the resin composition at 180°C for 30 minutes and then at 180°C for 60 minutes and the metal layer formed by plating is greater than 0.4 kgf / cm. [3] The resin composition as described in [1] or [2], wherein the content of component (C) is 85% by mass or more when the non-volatile components in the resin composition are 100% by mass. [4] The resin composition as described in any one of [1] to [3], wherein the component (C) contains aluminum oxide. [5] A resin composition as described in any one of [1] to [4], wherein component (C) is surface-treated with an aminosilane coupling agent. [6] A resin composition as described in any one of [1] to [5], wherein component (C) is surface-treated with N-phenyl-3-aminoalkyltrimethoxysilane. [7] A resin composition as described in any one of [1] to [6], wherein the thermal conductivity of the cured product obtained by thermally curing the resin composition at 180°C for 90 minutes is greater than 1.5 W / m·K and less than 5.0 W / m·K. [8] A resin composition as described in any one of [1] to [7], wherein component (A) is one or more selected from a resin having a glass transition temperature of 25°C or less and a resin that is liquid at 25°C. [9] A resin composition as described in any one of [1] to [8], wherein component (A) has a functional group that can react with component (B).

[10] A resin composition as described in any one of [1] to [9], wherein component (A) has one or more functional groups selected from the group consisting of a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group.

[11] A resin composition as described in any one of [1] to

[10] , wherein component (A) has an imide structure.

[12] A resin composition as described in any one of [1] to

[11] , wherein component (A) has a phenolic hydroxyl group.

[13] A resin composition as described in any one of [1] to

[12] , wherein component (A) has a polybutadiene structure and a phenolic hydroxyl group.

[14] The resin composition as described in any one of [1] to

[13] , which is a resin composition for an insulating layer of a semiconductor chip package.

[15] The resin composition as described in any one of [1] to

[14] is a resin composition for an insulating layer of a circuit substrate in which a circuit is formed using a semi-additive process.

[16] A resin sheet characterized by comprising: a support body, and a resin composition layer disposed on the support body and comprising the resin composition described in any one of [1] to

[15] .

[17] A circuit substrate characterized by comprising: an insulating layer formed by a cured product of the resin composition described in any one of [1] to

[15] .

[18] A semiconductor chip package, characterized by comprising: a circuit substrate as described in

[17] , and a semiconductor chip mounted on the aforementioned circuit substrate.

[19] A semiconductor chip package, characterized by comprising: a semiconductor chip sealed by the resin composition described in any one of [1] to

[15] , or the resin sheet described in

[16] . [Effects of the Invention]

[0010] According to the present invention, a resin composition is provided that can form a cured product having excellent thermal conductivity, excellent adhesion to metal layers, particularly metal layers formed by plating, and a balanced approach to suppressing warpage generated during the formation of an insulating layer; and a resin sheet, a circuit substrate, and a semiconductor chip package using the resin composition. Simple diagram description

[0011] [FIG. 1] FIG. 1 is a schematic cross-sectional view illustrating an example of a semiconductor chip package (Fan-out type WLP) according to the present invention. Implementation Method

[0012] The following describes in detail the resin composition, resin sheet, circuit substrate, and semiconductor chip package of the present invention.

[0013] [Resin composition] The resin composition of the present invention comprises: (A) a polymer compound having one or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkylene oxide structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure; (B) an epoxy resin; (C) a thermally conductive filler; and (D) an active ester hardener.

[0014] A resin composition containing components (A), (B), (C), and (D) can produce an insulating layer with excellent thermal conductivity, peel strength against metal layers, and excellent warpage suppression. Furthermore, the resin composition typically has a low melt viscosity. The resin composition may further contain (E) a hardener, (F) a hardening accelerator, (G) an inorganic filler (excluding those corresponding to component (C)), and (H) a flame retardant, if necessary. The following describes the components of the resin composition in detail.

[0015] <(A) A polymer compound having one or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkylene oxide structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure> The resin composition contains: (A) a polymer compound having one or more structures selected from the group consisting of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkylene oxide structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure. The inclusion of a polymer compound having these structures in the resin composition can suppress warping of the cured product. Furthermore, "(meth)acrylate" refers to both methacrylate and acrylate.

[0016] More specifically, the component (A) is composed of a polybutadiene structure such as polybutadiene and hydrogenated polybutadiene, a polysiloxane structure such as polysilicone rubber, a poly(meth)acrylate structure, a polyalkylene structure (preferably a polyalkylene structure having 2 to 15 carbon atoms, more preferably a polyalkylene structure having 3 to 10 carbon atoms, and more preferably a polyalkylene structure having 5 to 6 carbon atoms), a polyalkylene oxide structure (preferably a polyalkylene oxide structure having 2 to 15 carbon atoms, more preferably a polyalkylene oxide structure having 3 to 10 carbon atoms, and more preferably a polyalkylene oxide structure having 5 to 6 carbon atoms), or a polyalkylene oxide structure (preferably a polyalkylene oxide structure having 2 to 15 carbon atoms, more preferably a polyalkylene oxide structure having 3 to 10 carbon atoms, and more preferably a polyalkylene oxide structure having 5 to 6 carbon atoms). The present invention also provides a polyimide having a polyalkylene oxide structure having 5 to 6 carbon atoms (more preferably a polyalkylene oxide structure), a polyisoprene structure, a polyisobutylene structure, and one or more structures selected from polycarbonate structures. Preferably, the polyimide has one or more structures selected from polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure. More preferably, the polyimide has one or more structures selected from polybutadiene structure, polyisoprene structure, and polycarbonate structure.

[0017] Component (A) preferably has a high molecular weight for improved flexibility, with a number average molecular weight (Mn) preferably ranging from 1,000 to 1,000,000, and more preferably from 5,000 to 9,000,000. The number average molecular weight (Mn) is the polystyrene-equivalent number average molecular weight measured by GPC (gel permeation chromatography).

[0018] From the perspective of exhibiting flexibility, component (A) is preferably one or more resins selected from resins having a glass transition temperature (Tg) of 25°C or less and resins that are liquid at 25°C.

[0019] The glass transition temperature (Tg) of a resin having a glass transition temperature of 25°C or less is preferably 20°C or less, and more preferably 15°C or less. The lower limit of the glass transition temperature is not particularly limited, but is generally -15°C or greater. Furthermore, among resins that are liquid at 25°C, those that are liquid at 20°C or less are preferred, and those that are liquid at 15°C or less are more preferred.

[0020] From the perspective of improving the mechanical strength of the cured product, component (A) preferably has a functional group that reacts with component (B). Furthermore, functional groups that react with component (B) include, for example, functional groups that are generated by heating.

[0021] In a preferred embodiment, the functional groups reactive with component (B) are, for example, one or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. Among these functional groups, hydroxyl groups, acid anhydride groups, phenolic hydroxyl groups, epoxy groups, isocyanate groups, and urethane groups are preferred, with hydroxyl groups, acid anhydride groups, phenolic hydroxyl groups, and epoxy groups being more preferred, and phenolic hydroxyl groups being particularly preferred.

[0022] A preferred embodiment of component (A) is a butadiene resin. Among butadiene resins, those that are liquid at 25°C or have a glass transition temperature of 25°C or below are preferred. Preferred are at least one resin selected from the group consisting of resins containing a hydrogenated polybutadiene skeleton, butadiene resins containing hydroxyl groups, butadiene resins containing phenolic hydroxyl groups, butadiene resins containing carboxyl groups, butadiene resins containing acid anhydride groups, butadiene resins containing epoxy groups, butadiene resins containing isocyanate groups, and butadiene resins containing urethane groups. Butadiene resins containing phenolic hydroxyl groups are even more preferred. Examples of resins containing a hydrogenated polybutadiene skeleton include epoxy resins containing a hydrogenated polybutadiene skeleton. Butadiene resins containing phenolic hydroxyl groups include resins having a polybutadiene structure and phenolic hydroxyl groups.

[0023] The term "butadiene resin" herein refers to a resin containing a polybutadiene structure. In these resins, the polybutadiene structure may be contained in the main chain or in a side chain. The butadiene structure may be partially or fully hydrogenated. The term "resin containing a hydrogenated polybutadiene skeleton" herein refers to a resin in which at least a portion of the polybutadiene skeleton is hydrogenated, but does not necessarily mean that the polybutadiene skeleton is completely hydrogenated.

[0024] The number average molecular weight (Mn) of the butadiene resin is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, even more preferably 7,500 to 30,000, and particularly preferably 10,000 to 15,000. The number average molecular weight (Mn) of the resin is the polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

[0025] When the butadiene resin has functional groups, the functional group equivalent weight is preferably 100-10,000, more preferably 200-5,000. Furthermore, the functional group equivalent weight refers to the number of grams of resin containing one gram equivalent of functional groups. For example, the epoxy group equivalent weight can be measured according to JIS K7236. The hydroxyl group equivalent weight can be calculated by dividing the hydroxyl value measured according to JIS K1557-1 by the molecular weight of KOH.

[0026] Specific examples of butadiene resins include Ricon 657 (epoxy-containing polybutadiene), Ricon 130MA8, Ricon 130MA13, Ricon 130MA20, Ricon 131MA5, Ricon 131MA10, Ricon 131MA17, Ricon 131MA20, and Ricon 131MA17 manufactured by GLABARY. 184MA6" (polybutadiene containing anhydride groups), "JP-100" and "JP-200" (epoxidized polybutadiene) manufactured by Nippon Soda Co., Ltd., "GQ-1000" (polybutadiene with hydroxyl and carboxyl groups introduced), "G-1000", "G-2000", and "G-3000" (polybutadiene with hydroxyl groups at both ends), "GI-1000", "GI-2000", and "GI-3000" (hydrogenated polybutadiene with hydroxyl groups at both ends), "PB3600" and "PB4700" (epoxy compounds with polybutadiene skeletons) manufactured by DAICEL Co., Ltd., "EPFD A1005", "EPFD A1010", and "EPFD A1020" (epoxy compound of styrene, butadiene and styrene block copolymer), "FCA-061L" (epoxy compound with hydrogenated polybutadiene skeleton) and "R-45EPT" (epoxy compound with polybutadiene skeleton) manufactured by Nagase Chemical Co., Ltd.

[0027] In another preferred embodiment of component (A), a resin having an imide structure may be used. Examples of resins having an imide structure include hydroxyl-terminated polybutadiene, diisocyanate compounds, and linear polyimides made from tetrabasic anhydrides (such as those described in Japanese Patent Application Publication No. 2006-37083 and International Publication No. 2008 / 153208). The polybutadiene structure content of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be found in Japanese Patent Application Publication No. 2006-37083 and International Publication No. 2008 / 153208, which are incorporated herein by reference.

[0028] A preferred embodiment of component (A) is an isoprene resin. Specific examples of isoprene resins include "KL-610" and "KL-613" manufactured by Kuraray Co., Ltd. "Isoprene resin" refers to a resin containing a polyisoprene structure. In these resins, the polyisoprene structure may be contained in the main chain or in a side chain.

[0029] In a preferred embodiment, component (A) is a carbonate resin. Carbonate resins having a glass transition temperature of 25°C or lower are preferred, and at least one selected from the group consisting of hydroxyl-containing carbonate resins, phenolic hydroxyl-containing carbonate resins, carboxyl-containing carbonate resins, anhydride-containing carbonate resins, epoxy-containing carbonate resins, isocyanate-containing carbonate resins, and urethane-containing carbonate resins are preferred. "Carbonate resin" refers to a resin containing a polycarbonate structure. In these resins, the polycarbonate structure may be contained in the main chain or in a side chain.

[0030] The number average molecular weight (Mn) of the carbonate resin and the functional group equivalent weight when having a functional group are the same as those of the butadiene resin, and the preferred range is also the same.

[0031] Specific examples of carbonate resins include "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Chemicals Corporation, and "C-1090", "C-2090", and "C-3090" (polycarbonate diols) manufactured by Kuraray Corporation.

[0032] Alternatively, hydroxyl-terminated polycarbonates, diisocyanate compounds, and linear polyimides made from tetrabasic anhydrides can be used. The polycarbonate structure content of the polyimide resin is preferably 60% to 95% by mass, more preferably 75% to 85% by mass. Details of the polyimide resin can be found in International Publication No. 2016 / 129541, which is incorporated herein by reference.

[0033] Another preferred embodiment of component (A) is an acrylic resin. The acrylic resin is preferably one having a glass transition temperature (Tg) of 25°C or lower. More preferably, it is one or more resins selected from the group consisting of hydroxyl-containing acrylic resins, phenolic hydroxyl-containing acrylic resins, carboxyl-containing acrylic resins, anhydride-containing acrylic resins, epoxy-containing acrylic resins, isocyanate-containing acrylic resins, and urethane-containing acrylic resins. "Acrylic resin" refers to a resin containing a poly(meth)acrylate structure. In these resins, the poly(meth)acrylate structure may be contained in the main chain or in a side chain.

[0034] The number average molecular weight (Mn) of the acrylic resin is preferably 10,000 to 1,000,000, more preferably 30,000 to 900,000. The number average molecular weight (Mn) of the resin is the polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

[0035] When the acrylic resin has a functional group, the equivalent weight of the functional group is preferably 1,000 to 50,000, more preferably 2,500 to 30,000.

[0036] Specific examples of acrylic resins include Densireni "SG-70L", "SG-708-6", "WS-023", "SG-700AS", and "SG-280TEA" manufactured by Nagase Chemical Co., Ltd. (carboxyl group-containing acrylic copolymer resins, acid value 5-34 mgKOH / g, weight average molecular weight 400,000-900,000, Tg -30-5°C), "SG-80H", "SG-80H-3", and "SG-P3" (epoxy group-containing acrylic copolymer resins, epoxy equivalent 4761-14285 g / eq, weight average molecular weight 200-300°C). 350,000~850,000, Tg11~12℃), "SG-600TEA", "SG-790" (hydroxyl-containing acrylate copolymer resin, hydroxyl value 20~40mgKOH / g, weight average molecular weight 500,000~1.2 million, Tg-37~-32℃), "ME-2000" and "W-116.3" (carboxyl-containing acrylate copolymer resin), "W-197C" (hydroxyl-containing acrylate copolymer resin), "KG-25", "KG-3000" (epoxy-containing acrylate copolymer resin), etc. manufactured by Negami Industries.

[0037] In another preferred embodiment of component (A), silicone resin, alkyl resin, alkoxy resin, or isobutylene resin is used.

[0038] Specific examples of silicone resins include "SMP-2006," "SMP-2003PGMEA," and "SMP-5005PGMEA" manufactured by Shin-Etsu Polysilicone Co., Ltd., amino-terminated polysiloxanes, and linear polyimides made from tetrabasic anhydrides (International Publication No. 2010 / 053185). "Silicone resin" refers to a resin containing a polysiloxane structure. In these resins, the polysiloxane structure can be contained in the main chain or in a side chain.

[0039] Specific examples of alkyl resins and alkoxy resins include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Corporation, "YX-7180" manufactured by Mitsubishi Chemical Corporation (a resin containing an alkylene structure with an ether bond), "EXA-4850-150," "EXA-4816," and "EXA-4822" manufactured by DIC Corporation, "EP-4000," "EP-4003," "EP-4010," and "EP-4011" manufactured by Adeka Corporation, "BEO-60E" and "BPO-20E" manufactured by Shin Nippon Chemical Co., Ltd., and "YL7175" and "YL7410" manufactured by Mitsubishi Chemical Corporation. "Alkyl resin" refers to a resin containing a polyalkylene structure, and "alkoxy resin" refers to a resin containing a polyalkylene oxide structure. In these resins, the polyalkylene structure and the polyalkylene oxide structure may be contained in the main chain or in the side chain.

[0040] Specific examples of isobutylene resins include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation. "Isobutylene resin" refers to a resin containing a polyisobutylene structure. In these resins, the polyisobutylene structure may be contained in the main chain or in a side chain.

[0041] Another preferred embodiment of component (A) includes, for example, acrylic rubber particles, polyamide particles, and silicone particles. Specific examples of acrylic rubber particles include particles of organic solvent-insoluble and non-melting resins, formed by chemically crosslinking a rubber-elastic resin such as acrylonitrile-butadiene rubber, butadiene rubber, or acrylic rubber. Specific examples include XER-91 (manufactured by Japan Synthetic Rubber Co., Ltd.), SHUFFLE AC3355, AC3816, AC3832, AC4030, AC3364, and IM101 (all manufactured by Kanz Chemicals Co., Ltd.), and PARALOID EXL2655 and EXL2602 (all manufactured by Kureha Chemical Industries, Ltd.). Specific examples of polyamide particles include aliphatic polyamides such as nylon, and any polyamide-imide-based particles having a flexible skeleton can be used. Specifically, for example, VESTOSINT 2070 (manufactured by DAICELHULS) or SP500 (manufactured by Toray Industries, Ltd.)

[0042] From the perspective of imparting flexibility, the content of component (A) in the resin composition is preferably 65% ​​by mass or less, more preferably 60% by mass or less, particularly preferably 55% by mass or less, and most preferably 50% by mass or less, based on 100% by mass of the non-volatile components (resin component) of the resin composition excluding components (C) and (G). Furthermore, the lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, and most preferably 25% by mass or more.

[0043] <(B) Epoxy Resin> The resin composition of the present invention contains an epoxy resin as component (B). To further enhance the effects of the present invention, component (B) is preferably an epoxy resin having an aromatic structure. Aromatic structures generally refer to chemical structures defined as aromatic, and also include polycyclic aromatics and aromatic heterocycles.

[0044] Epoxy resins, for example, bicyclopentadiene epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AF epoxy resins, dicyclopentadiene epoxy resins, trisphenol epoxy resins, naphthol-novolac epoxy resins, phenol-novolac epoxy resins, tert-butyl-catechol epoxy resins, naphthalene epoxy resins, naphthol epoxy resins, anthracene epoxy resins, glycidylamine epoxy resins with aromatic structures, glycidylester epoxy resins with aromatic structures Epoxy resins include cresol-novolac epoxy resins, biphenyl epoxy resins, linear aliphatic epoxy resins with aromatic structures, aromatic epoxy resins with butadiene structures, aromatic alicyclic epoxy resins, heterocyclic epoxy resins, aromatic epoxy resins containing spiro rings, aromatic cyclohexanedimethanol epoxy resins, naphthyl ether epoxy resins, aromatic trimethylol epoxy resins, tetraphenylethane epoxy resins, and aminophenol epoxy resins. Epoxy resins may be used alone or in combination. Component (B) is preferably one or more selected from bisphenol A epoxy resins, bisphenol F epoxy resins, aminophenol epoxy resins, and naphthalene epoxy resins.

[0045] Epoxy resins preferably contain two or more epoxy groups per molecule. It is also preferred that, based on 100% by mass of the non-volatile content of the epoxy resin, at least 50% by mass of the epoxy resin contain two or more epoxy groups per molecule. Among these, epoxy resins preferably contain two or more epoxy groups per molecule that are liquid at 20°C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that contain three or more epoxy groups per molecule that are solid at 20°C (hereinafter referred to as "solid epoxy resins"). The combined use of a liquid epoxy resin and a solid epoxy resin can produce a resin composition with excellent flexibility. Furthermore, the fracture strength of the cured resin composition can be increased.

[0046] Liquid epoxy resins, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin with an aromatic structure, glycidyl amine epoxy resin with an aromatic structure, phenol-novolac epoxy resin, alicyclic epoxy resin with an ester skeleton with an aromatic structure, cyclohexanedimethanol epoxy resin with an aromatic structure, aminophenol epoxy resin, and epoxy resin with a butadiene structure with an aromatic structure are preferred; bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, aminophenol epoxy resin, and naphthalene epoxy resin are more preferred; bisphenol A epoxy resin, bisphenol F epoxy resin, and aminophenol epoxy resin are more preferred. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation, "828US" and "jER828EL" (bisphenol A-type epoxy resins), "jER806" and "jER807" (bisphenol F-type epoxy resins) manufactured by Mitsubishi Chemical Corporation, "jER152" (phenol-novolac-type epoxy resins), "630" (aminophenol-type epoxy resins), and "630LSD" (glycidylamine-type epoxy resins) manufactured by Nippon Steel & Sumikin Chemicals, "ZX1059" (a mixture of bisphenol A-type epoxy resins and bisphenol F-type epoxy resins), "EX-721" (glycidyl ester-type epoxy resins) manufactured by Nagase Chemical, and "CELLOXIDE" manufactured by Daicel. Examples include "ZX2021P" (an alicyclic epoxy resin with an ester skeleton), "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical Co., Ltd. (liquid 1,4-glycidylcyclohexane), and "YX7400" (a high-resilience epoxy resin) manufactured by Mitsubishi Chemical Corporation. These can be used alone or in combination.

[0047] Solid epoxy resins include, for example, bixylenol epoxy resins, naphthalene tetrafunctional epoxy resins, cresol-novolac epoxy resins, dicyclopentadiene epoxy resins, trisphenol epoxy resins, naphthol epoxy resins, biphenyl epoxy resins, naphthalene ether epoxy resins, anthracene epoxy resins, bisphenol A epoxy resins, bisphenol AF epoxy resins, and tetraphenylethane epoxy resins. Bixylenol epoxy resins, naphthalene tetrafunctional epoxy resins, naphthol epoxy resins, biphenyl epoxy resins, and naphthalene ether epoxy resins are more preferred. Bixylenol epoxy resins, naphthalene tetrafunctional epoxy resins, naphthalene ether epoxy resins, and biphenyl epoxy resins are even more preferred. Specific examples of solid epoxy resins include DIC Corporation's "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), "N-690" (cresol-novolac-type epoxy resin), "N-695" (cresol-novolac-type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", "HP-7200HHH" (dicyclopentadiene-type epoxy resin), "EXA7311 ", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthyl ether type epoxy resin), "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol-novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. 、"ESN485" (naphthol-phenol novolac type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin), "YX4000HK" (biphenyl type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" ( Solid bisphenol A-type epoxy resin), "jER1031S" (tetraphenylethane-type epoxy resin), "157S70" (bisphenol-novolac-type epoxy resin), Mitsubishi Chemical Corporation's "YX4000HK" (bimethylol-type epoxy resin), "YX8800" (anthracene-type epoxy resin), Osaka Gas Chemical Co., Ltd.'s "PG-100" and "CG-500," Mitsubishi Chemical Corporation's "YL7800" (fluorene-type epoxy resin), and Mitsubishi Chemical Corporation's "jER1031S" (tetraphenylethane-type epoxy resin) are examples of these. These can be used alone or in combination of two or more.

[0048] When using a liquid epoxy resin and a solid epoxy resin in component (B), the mass ratio (solid epoxy resin: liquid epoxy resin) is preferably in the range of 1:0.1 to 1:15. A mass ratio of the liquid epoxy resin to the solid epoxy resin within this range can achieve the following benefits: i) adequate adhesion when used in the form of a resin sheet; ii) sufficient flexibility when used in the form of a resin sheet, improving handling; and iii) a cured product with sufficient breaking strength. To consider the above effects i) to iii), the mass ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin: liquid epoxy resin) is preferably in the range of 1:0.3 to 1:10, and more preferably in the range of 1:0.6 to 1:8.

[0049] From the perspective of producing an insulating layer with excellent mechanical strength and insulation reliability, the epoxy resin content in the resin composition is preferably 1% by mass or greater, more preferably 2% by mass or greater, and particularly preferably 3% by mass or greater, based on 100% by mass of the non-volatile component in the resin composition. The upper limit of the epoxy resin content is not particularly limited as long as the effects of the present invention are achieved, but is preferably 10% by mass or less, more preferably 8% by mass or less, and particularly preferably 6% by mass or less.

[0050] Furthermore, the epoxy resin content in the resin composition is preferably 20% by mass or greater, more preferably 25% by mass or greater, and particularly preferably 30% by mass or greater, based on 100% by mass of the non-volatile content of the resin composition after excluding components (C) and (G), in order to produce an insulating layer having good mechanical strength and insulation reliability. The upper limit of the epoxy resin content is not particularly limited as long as the effects of the present invention are achieved, but is preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 55% by mass or less.

[0051] The epoxy equivalent weight of the epoxy resin is preferably 50-5000, more preferably 50-3000, particularly preferably 80-2000, and most preferably 110-1000. Within this range, an insulating layer with sufficient crosslinking density with the cured product and minimal surface roughness can be produced. The epoxy equivalent weight can be measured according to JIS K7236 and is the mass of the resin containing one equivalent of epoxy groups.

[0052] The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and particularly preferably 400 to 1500. The weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC).

[0053] <(C) Thermally Conductive Filler> The resin composition of the present invention comprises (C) a thermally conductive filler. In this specification, the thermally conductive filler refers to an inorganic filler having a thermal conductivity of 20 W / m·K or greater.

[0054] The material of component (C) is not particularly limited as long as its thermal conductivity is within the above range. Examples of materials comprising component (C) include aluminum oxide, aluminum nitride, boron nitride, and silicon carbide. Among these, aluminum oxide is particularly preferred. Component (C) may be used alone or in combination of two or more. Furthermore, two or more of the same material may be used in combination.

[0055] The average particle size of component (C) is preferably 5 μm or less, more preferably 4 μm or less, and particularly preferably 3 μm or less, from the perspective of producing an insulating layer with both excellent thermal conductivity and peel strength, and from the perspective of improving fillability. Furthermore, it is preferably 0.1 μm or greater, more preferably 1.0 μm or greater, and particularly preferably 1.5 μm or greater. The average particle size of component (C) can be measured using the laser diffraction scattering method based on Mie scattering theory. Specifically, for example, a volume-based particle size distribution of the inorganic filler is generated using a laser diffraction scattering particle size distribution analyzer, and the median number diameter is used as the average particle size. The measurement sample is preferably one in which component (C) is ultrasonically dispersed in water. Examples of laser diffraction scattering particle size distribution analyzers include the LA-500 manufactured by Horiba, Ltd. and the SALD2200 manufactured by Shimadzu Corporation. Specifically, for example, it can be measured by the method described in <Measurement of Average Particle Diameter of Thermally Conductive Filler> described later.

[0056] The specific surface area of ​​the (C) component is preferably 0.5 m² / g or greater, in order to achieve both excellent thermal conductivity and peel strength in the insulation layer and to improve fillability. The specific surface area of ​​the (C) component is preferably between 0.5 m² / g and 10 m² / g, and more preferably between 0.5 m² / g and 5 m² / g. The specific surface area of ​​the (C) component can be measured using the nitrogen BET method. Specifically, for example, an automatic specific surface area measuring device such as the "Macsorb HM-1210" manufactured by MOUNTECH can be used. Specifically, for example, the specific surface area can be measured using the method described below in "Measurement of the Specific Surface Area of ​​the Thermally Conductive Filler."

[0057] From the perspective of improving moisture resistance and dispersibility, component (C) may be treated with a surface treatment agent such as one or more aminosilane coupling agents, epoxysilane coupling agents, sulfhydrylsilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, or titanate coupling agents. Commercially available surface treatment agents include Shin-Etsu Chemical's "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical's "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical's "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical's "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical's "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane), Shin-Etsu Chemical's "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical's "KBM103" (phenyltrimethoxysilane), and Shin-Etsu Chemical's "KBM-4803" (long-chain epoxy-type silane coupling agent). From the perspective of reducing melt viscosity and improving lamination properties, component (C) preferably undergoes surface treatment with an aminosilane-based coupling agent. It is particularly preferred to use N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminooctyltrimethoxysilane, or N-phenyl-3-aminoalkyltrimethoxysilane for surface treatment, and even more preferred is N-phenyl-3-aminooctyltrimethoxysilane for surface treatment.

[0058] From the perspective of obtaining an insulating layer having both excellent thermal conductivity and peel strength, the content of component (C) is preferably 85% by mass or greater, more preferably 88% by mass or greater, and particularly preferably 89% by mass or greater, or 90% by mass or greater, based on 100% by mass of the non-volatile components in the resin composition. The upper limit is preferably 95% by mass or less, more preferably 93% by mass or less, and particularly preferably 92% by mass or less.

[0059] <(D) Active Ester Hardener> The resin composition of the present invention includes (D) an active ester hardener. The active ester hardener is not particularly limited, but generally preferred are compounds having two or more phenolic esters, thiophenolic esters, N-hydroxylamine esters, or esters of heterocyclic hydroxyl compounds, each molecule containing highly reactive ester groups. The active ester hardener is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxyl compound and / or a thiol compound. In particular, from the perspective of improving heat resistance, active ester hardeners obtained from a carboxylic acid compound and a hydroxyl compound are preferred, and those obtained from a carboxylic acid compound and a phenolic compound and / or a naphthol compound are particularly preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Phenol compounds or naphthol compounds, such as hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compounds, phenol-novolac, etc. "Dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0060] Specifically, for example, active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated phenol-novolacs, and active ester compounds containing benzoylated phenol-novolacs are preferred. Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are particularly preferred. A "dicyclopentadiene-type diphenol structure" refers to a divalent structure formed by a phenylene group, a dicyclopentylene group, and a phenylene group.

[0061] Active ester compounds may be used, for example, those disclosed in Japanese Patent Application Publication No. 2004-277460 and Japanese Patent Application Publication No. 2013-40270, or commercially available active ester compounds. Among commercially available active ester curing agents, active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451," "EXB9460," "EXB9460S," "HPC-8000-65T," "HPC-8000H-65TM," and "EXB-8000L-65TM" (manufactured by DIC Corporation); active ester compounds containing a naphthalene structure, such as "EXB9416-70BK" (manufactured by DIC Corporation); active ester compounds containing an acetylated phenol-novolac, such as "DC808" (manufactured by Mitsubishi Chemical Corporation); Active ester curing agents containing benzoyl compounds of phenol-novolacs, such as "YLH1026" (manufactured by Mitsubishi Chemical Corporation); active ester curing agents containing acetylated phenol-novolacs, such as "DC808" (manufactured by Mitsubishi Chemical Corporation); active ester curing agents containing benzoyl compounds of phenol-novolacs, such as "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation); and "EXB9050L-62M" (phosphorus atom-containing active ester compound) manufactured by DIC Corporation.

[0062] The content of component (D) is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less, based on 100% by mass of the non-volatile components in the resin composition. While the lower limit is not particularly limited, it is generally preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. When the content of component (D) is within this range, thermal conductivity and peel strength can be improved.

[0063] <(E) Hardener> The resin composition of the present invention may contain a hardener (E) in addition to the component (D). The component (E) referred to herein does not include the active ester hardener (D). The hardener (E) is not particularly limited as long as it has the function of hardening the resin (B) component. Examples include phenolic hardeners, naphthol hardeners, benzoxazoline hardeners, and the like. The hardener may be a single hardener, or a combination of two or more. Component (D) is preferably one or more selected from the group consisting of a phenolic hardener, a naphthol hardener, and a cyanate hardener, with one or more selected from the group consisting of a phenolic hardener being even more preferred.

[0064] Phenol hardeners and naphthol hardeners are preferably phenolic hardeners with a novolac structure or naphthol hardeners with a novolac structure from the perspective of heat resistance and water resistance. In addition, nitrogen-containing phenolic hardeners are preferably phenolic hardeners with a three-component structure from the perspective of adhesion to the wiring layer. Among them, the use of a phenolic hardener containing three A phenol-novolac hardener for the backbone is preferred.

[0065] Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals, "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd., and "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", and "SN485" manufactured by Nippon Steel & Sumitomo Metal Corporation. SN395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165" manufactured by DIC Corporation, "GDP-6115L", "GDP-6115H" manufactured by Qun Rong Chemical Co., Ltd., etc.

[0066] Benzoxazone Specific examples of the hardener include "HFB2006M" manufactured by Showa High Polymer Co., Ltd., "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0067] Cyanate ester curing agents, for example, bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylidene-1,5-phenylene cyanate), 4,4'-methylidenebis(2,6-xylylene cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-xylylene)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol-novolac and cresol-novolac, and these cyanate resins partially trihydrated Specific examples of cyanate ester hardeners include "PT30" and "PT60" manufactured by LONZA JAPAN (both are phenol-novolac type multifunctional cyanate resins), "BA230", and "BA230S75" (partial or complete tri-cyanate of bisphenol A dicyanate). to form a terpolymer) etc.

[0068] Specific examples of carbodiimide-based hardeners include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

[0069] When the resin composition contains component (E), the content of component (E) in the resin composition is not particularly limited. However, the content is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 2% by mass or less, based on 100% by mass of the non-volatile component in the resin composition. The lower limit is not particularly limited, but is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more.

[0070] <(F) Hardening Accelerator> The resin composition of the present invention includes (F) a hardening accelerator. Examples of such hardening accelerators include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators. Phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, with amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators being particularly preferred. Each hardening accelerator may be used alone or in combination.

[0071] Phosphorus-based hardening accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenyl boride, n-butylphosphonium tetraphenyl boride, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0072] Amine-based hardening accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0073] Imidazole hardening accelerators, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-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-undecylimidazole salt trimellitate, 1-cyanoethyl-2-phenylimidazole salt trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-trimethylimidazolium , 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-tri , 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-tri , 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tri Imidazole compounds such as 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-benzylimidazole chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

[0074] As the imidazole-based hardening accelerator, a commercially available product such as "P200-H50" manufactured by Mitsubishi Chemical Corporation may be used.

[0075] Guanidine-based hardening accelerators include, for example, 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-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine. Dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

[0076] Metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonikel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0077] When the resin composition contains component (F), the content of component (F) in the resin composition is not particularly limited, but is preferably 0.01% to 1% by mass when the non-volatile component in the resin composition is 100% by mass.

[0078] <(G) Inorganic fillers (excluding those corresponding to (C))> The resin composition of the present invention may include (G) an inorganic filler. The inorganic filler (G) referred to herein does not include the filler corresponding to (C) a thermally conductive filler. The material of component (G) is not particularly limited and includes, for example, silica, glass, cordierite, silicate, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, diaspore, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Spherical silica is preferred. The inorganic filler may be used alone or in combination of two or more.

[0079] The average particle size of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, particularly preferably 2.2 μm or less, and even more preferably 2 μm or less, from the perspective of achieving an insulating layer with high circuit embeddability and low surface roughness. The lower limit of this average particle size is not particularly limited, but is preferably 0.01 μm or greater, more preferably 0.05 μm or greater, and particularly preferably 0.1 μm or greater. The average particle size of the inorganic filler can be measured using the same method as for component (C). Commercially available inorganic fillers having these average particle sizes include, for example, "YC100C," "YA050C," "YA050C-MJE," and "YA010C" manufactured by ADMATECHS, "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., "Silfile NSS-3N," "Silfile NSS-4N," and "Silfile NSS-5N" manufactured by Tokuyama Corporation, and "SC2500SQ," "SO-C6," "SO-C4," "SO-C2," and "SO-C1" manufactured by ADMATECHS.

[0080] To improve moisture resistance and dispersibility, inorganic fillers are preferably treated with one or more surface treatment agents such as aminosilane coupling agents, epoxysilane coupling agents, sulfhydrylsilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. Specific commercially available surface treatment agents are listed above.

[0081] When the resin composition contains component (G), the content of component (G) in the resin composition is not particularly limited. However, the content is preferably 0.1% by mass or greater, more preferably 0.5% by mass or greater, and particularly preferably 1% by mass or greater, based on 100% by mass of the non-volatile component in the resin composition. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and particularly preferably 3% by mass or less.

[0082] <(H) Flame retardant> The resin composition may contain (H) a flame retardant. Examples of flame retardants include organophosphorus flame retardants, phosphorus compounds containing organic nitrogen, nitrogen compounds, polysilicone flame retardants, and metal hydroxides. These flame retardants may be used alone or in combination.

[0083] As flame retardants, commercially available products such as "HCA-HQ" manufactured by Sanguang Company may also be used.

[0084] When the resin composition contains a flame retardant, the content of the component (H) is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it is preferably 0.5% to 10% by mass, more preferably 0.5% to 5% by mass, and particularly preferably 0.5% to 3% by mass.

[0085] <(I) Optional Additives> The resin composition may contain other additives, if necessary, such as organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds, and resin additives such as binders, tackifiers, defoamers, leveling agents, adhesion-imparting agents, and colorants.

[0086] <Physical Properties of Resin Composition> The resin composition of the present invention, when heat-cured at 180°C for 30 minutes and then at 180°C for 60 minutes, exhibits excellent peel strength against metal layers, particularly metal layers formed by plating. This allows the formation of an insulating layer with excellent peel strength. Specifically, the resin composition of the present invention, after heat-treating at 180°C for 30 minutes, can be plated onto the roughened surface of the roughened surface. After heat-treating at 180°C for 60 minutes, the cured product exhibits excellent peel strength against the metal layer. The peel strength is preferably 0.4 kgf / cm or greater, more preferably 0.45 kgf / cm or greater, and particularly preferably 0.5 kgf / cm or greater. The upper limit of the peel strength is not particularly limited, but is generally 1.5 kgf / cm or less, 1 kgf / cm or less, etc. The peel strength can be evaluated according to the method described below in <Measurement and Evaluation of the Tensile Peel Strength of the Metal Layer (Peel Strength)>. The metal layer is preferably a metal layer containing copper, and more preferably a metal layer formed by plating.

[0087] The resin composition of the present invention exhibits excellent thermal conductivity after thermal curing at 180°C for 90 minutes. This provides an insulating layer with excellent thermal conductivity. The thermal conductivity is preferably 1.5 W / m·K or higher, more preferably 1.8 W / m·K or higher, and particularly preferably 2.0 W / m·K or higher. The upper limit of the thermal conductivity is 5.0 W / m·K or lower, 4.0 W / m·K or lower, or 3.5 W / m·K or lower. Thermal conductivity can be evaluated using the method described below in "Measurement of Thermal Conductivity of Cured Material."

[0088] The cured resin composition of the present invention exhibits a low elastic modulus at 23°C after thermal curing at 180°C for 90 minutes. This results in an insulating layer with a low elastic modulus. The elastic modulus is preferably 25 GPa or less, more preferably 20 GPa or less, and particularly preferably 15 GPa or less. The lower limit is 0.1 GPa or greater. The elastic modulus can be measured according to the method described below in "Determination of Elastic Modulus."

[0089] The resin composition of the present invention exhibits low warpage after thermal curing at 100°C for 30 minutes and then at 180°C for 30 minutes. This results in an insulating layer with low warpage. The average warpage at each of the four corners is preferably less than 1 cm. Warpage can be measured using the method described below in "Warpage Evaluation."

[0090] The resin composition of the present invention exhibits low melt viscosity. This improves the lamination properties of the resin composition layer of the resin sheet described below, and allows the production of a cured resin composition with high peel strength. The melt viscosity is preferably 500 poise or higher, more preferably 1000 poise or higher, and particularly preferably 1500 poise or higher; and preferably 8500 poise or lower, more preferably 8000 poise or lower, and particularly preferably 7500 poise or lower, or 7000 poise or lower. The melt viscosity can be measured according to the method described below in "Determination of Melt Viscosity."

[0091] The resin composition of the present invention can produce an insulating layer with excellent thermal conductivity and peel strength. Therefore, the resin composition of the present invention is suitable for use as a resin composition for forming the insulating layer of semiconductor chip packages (resin composition for insulating layers of semiconductor chip packages), as a resin composition for forming the insulating layer of circuit substrates (including printed wiring boards) (resin composition for insulating layers of circuit substrates), and particularly suitable for use as a resin composition for forming an interlayer insulating layer on a substrate having a conductive layer formed by plating (resin composition for interlayer insulating layers of circuit substrates having a conductive layer formed by plating, i.e., a circuit substrate having circuits formed by a semi-additive process). Furthermore, the present invention is also suitable for use in resin compositions for sealing semiconductor wafers (resin compositions for semiconductor wafer sealing) and resin compositions for forming wiring on semiconductor wafers (resin compositions for forming semiconductor wafer wiring).

[0092] [Resin sheet] The resin sheet of the present invention comprises a support and a resin composition layer formed by the resin composition of the present invention disposed on the support.

[0093] From the perspective of thinning, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, and particularly preferably 100 μm or less, or 80 μm or less, 60 μm or less, 50 μm or less, or 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but is typically 1 μm or more, 5 μm or more, 10 μm or more, etc.

[0094] The support body can be, for example, a film formed of a plastic material, a metal foil, a release paper, etc., and a film formed of a plastic material or a metal foil is preferred.

[0095] When a film made of a plastic material is used as the support, the plastic material may include polyesters such as polyethylene terephthalate (hereinafter also referred to as "PET") and polyethylene naphthyl ester (hereinafter also referred to as "PEN"), polycarbonate (hereinafter also referred to as "PC"), acrylic esters such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among them, polyethylene terephthalate and polyethylene naphthyl ester are preferred, and the inexpensive polyethylene terephthalate is particularly preferred.

[0096] When a metal foil is used as the support, the metal foil may be, for example, copper foil or aluminum foil, with copper foil being preferred. The copper foil may be copper alone or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0097] The support may be subjected to matte treatment, corona treatment, etc. on the surface in contact with the resin composition layer.

[0098] Furthermore, a support with a release layer may be used, with the surface to which the resin composition layer is attached. The release agent used in the release layer of the support with a release layer may be, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may also be used for the support with a release layer, such as PET films having a release layer primarily composed of an alkyd resin release agent, such as Lindsay's "SK-1," "AL-5," and "AL-7," Toray's "RUMINA T60," Teijin's "PUREX," and UNITIKA's "YUNIPIRE."

[0099] The thickness of the support is not particularly limited, but is generally preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. Furthermore, when using a support with a release layer, the entire thickness of the support with the release layer is preferably within the above range.

[0100] The resin sheet can be produced, for example, by dissolving a resin composition in an organic solvent to prepare a resin coating, applying the resin coating to a support using a slit coater, a compression die method, or the like, and drying the coating to form a resin composition layer.

[0101] Organic solvents include, for example, 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; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. These organic solvents may be used alone or in combination.

[0102] Drying can be carried out using known methods such as heating and hot air blowing. Drying conditions are not particularly limited; generally, the resin composition layer is dried until the organic solvent content is 10% by mass or less, preferably 5% by mass or less. This varies depending on the boiling point of the organic solvent in the resin coating. For example, when using a resin coating containing 30% to 60% by mass of an organic solvent, drying at 50°C to 150°C for 3 to 10 minutes will form a resin composition layer.

[0103] A protective film may be laminated on the surface of the resin sheet not in contact with the support of the resin composition layer (i.e., the surface opposite the support). The thickness of the protective film is not particularly limited and may range from 1 μm to 40 μm, for example. Lamination with the protective film prevents impurities from adhering to and damaging the surface of the resin composition layer. The resin sheet can be stored in a roll. If the resin sheet has a protective film, the film can be removed before use.

[0104] Resin sheets are suitable for use in the process of forming insulating layers (insulating resin sheets for semiconductor chip packages) during the manufacturing of semiconductor chip packages. For example, resin sheets are suitable for forming insulating layers for circuit substrates (insulating resin sheets for circuit substrates), and are particularly suitable for forming interlayer insulating layers on substrates where conductive layers are formed by plating (interlayer insulating layers for circuit substrates where conductive layers are formed by plating). Examples of packages using these substrates include FC-CSP, MIS-BGA, and ETS-BGA packages.

[0105] Resin sheets are also suitable for use in sealing semiconductor wafers (resin sheets for semiconductor wafer sealing) or forming wiring on semiconductor wafers (resin sheets for semiconductor wafer wiring formation), such as fan-out WLPs (wafer level packages), fan-in WLPs, fan-out PLPs (panel level packages), and fan-in PLPs. They are also suitable for use in MUF (molding under filling) materials used to connect semiconductor chips to substrates. Resin sheets are also suitable for a wide range of other applications requiring high insulation reliability, such as forming the insulating layer of circuit substrates for printed wiring boards.

[0106] In addition to the resin sheet, a prepreg formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention can also be used.

[0107] The sheet-like fiber substrate used in the prepreg is not particularly limited; commonly used prepreg substrates include glass fiber cloth, aromatic polyamide nonwoven fabric, and liquid crystal polymer nonwoven fabric. To minimize thickness, the sheet-like fiber substrate is preferably 900 μm or less, more preferably 800 μm or less, particularly preferably 700 μm or less, and most preferably 600 μm or less. The lower limit of the sheet-like fiber substrate thickness is not particularly limited, but is typically 1 μm or greater, 1.5 μm or greater, or 2 μm or greater.

[0108] The prepreg can be prepared by a known method such as a hot melt adhesive method or a solvent method.

[0109] The thickness of the prepreg may also be in the same range as that of the resin composition layer in the above-mentioned resin sheet.

[0110] [Circuit board] The circuit substrate of the present invention is an insulating layer formed by a cured product containing the resin composition of the present invention. The manufacturing method of the circuit substrate of the present invention comprises: (1) preparing a substrate and a substrate with a wiring layer having a wiring layer provided on at least one side of the substrate; (2) laminating the resin sheet of the present invention on a substrate with a wiring layer in such a manner that the wiring layer is embedded in the resin composition layer, and forming an insulating layer by heat curing. (3) A step of forming a connection between the wiring layers. In addition, the method for manufacturing a circuit substrate may also include a step of (4) removing the base material.

[0111] In step (3), there is no particular limitation as long as the method can form a connection between the wiring layers. Preferably, the method includes forming a via hole in the insulating layer to form the wiring layer, and polishing or grinding the insulating layer to expose the wiring layer.

[0112] <Step (1)> Step (1) is a step of preparing a substrate and a substrate with a wiring layer having a wiring layer provided on at least one side of the substrate. Typically, the substrate with a wiring layer has a first metal layer and a second metal layer on both sides of the substrate, which are parts of the substrate, and the wiring layer is formed on the side opposite to the substrate side of the second metal layer. Specifically, a dry film (photosensitive resist film) is laminated on the substrate, and exposed and developed under specific conditions using a photomask to form a patterned dry film. The developed patterned dry film is used as a plating mask, and after forming the wiring layer by electrolytic plating, the patterned dry film is peeled off. Alternatively, the substrate may not have the first metal layer and the second metal layer.

[0113] Substrates such as glass epoxy substrates, metal substrates (such as stainless steel or cold-rolled steel (SPCC)), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates may also have a metal layer such as copper foil formed on the substrate surface. Furthermore, a removable first metal layer and a second metal layer (such as Mitsui Kinzoku's ultra-thin copper foil with a carrier, tradename "Micro Thin") may also be formed on the surface.

[0114] The dry film is not particularly limited as long as it is a photosensitive dry film formed from a photoresist composition. For example, a dry film made of a novolac resin or an acrylic resin can be used. Commercially available dry films can also be used.

[0115] The lamination conditions of the substrate and the dry film are the same as those of the lamination in the step (2) described later in which the resin sheet is embedded in the wiring layer, and the preferred range is also the same.

[0116] After the dry film is laminated on the substrate, a photomask can be used to form the desired pattern on the dry film, and exposure and development can be performed according to specific conditions.

[0117] The line (line width) / space (width between lines) ratio of the wiring layer is not particularly limited, but is preferably 20 / 20 μm or less (i.e., a pitch of 40 μm or less), more preferably 10 / 10 μm or less, particularly preferably 5 / 5 μm or less, extremely preferably 1 / 1 μm or less, and most preferably 0.5 / 0.5 μm or greater. The pitch does not need to be uniform across all wiring layers. The minimum pitch in the wiring layer can be 40 μm or less, 36 μm or less, or even 30 μm or less.

[0118] After forming the dry film pattern, the wiring layer is formed and the dry film is peeled off. The wiring layer can be formed by using the dry film formed with the desired pattern as a plating mask and then performing the plating process.

[0119] The conductor material used in the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The wiring layer may be a single metal layer or an alloy layer. For example, an alloy layer may be formed of an alloy of two or more metals selected from the aforementioned group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). From the perspectives of versatility, cost, and ease of patterning in forming the wiring layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferred. A single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferred. A single metal layer of copper is even more preferred.

[0120] The thickness of the wiring layer is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, and particularly preferably 10 to 20 μm, or 15 to 20 μm, depending on the desired design of the wiring board. In step (3), when the insulating layer is polished or ground to expose the wiring layer and the wiring layer is connected between layers, the thickness of the wiring connected between layers is preferably different from that of the wiring not connected. The thickness of the wiring layer can be adjusted by repeating the aforementioned patterning step. The thickness of the thickest wiring layer (conductive support) in each wiring layer is preferably not less than 2 μm and not more than 100 μm, depending on the desired design of the wiring board. The wiring connected between layers can also be convex in shape.

[0121] After forming the wiring layer, the dry film is peeled off. For example, the dry film can be peeled off using an alkaline stripping solution such as sodium hydroxide solution. If necessary, the unwanted wiring pattern can be removed by etching, etc., to form the desired wiring pattern. The spacing between the formed wiring layers is as described above.

[0122] <Step (2)> Step (2) is a step of laminating the resin sheet of the present invention onto a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer, and then thermally curing the laminate to form an insulating layer. Specifically, the wiring layer of the substrate with a wiring layer obtained in step (1) is laminated so that the wiring layer is embedded in the resin composition layer of the resin sheet, and then thermally curing the resin composition layer of the resin sheet to form an insulating layer.

[0123] The wiring layer and resin sheet can be laminated by, for example, heat-pressing the resin sheet against the wiring layer from the support side after removing the protective film from the resin sheet. The member for heat-pressing the resin sheet against the wiring layer (hereinafter referred to as the "heat-pressing member") can be, for example, a heated metal plate (such as a SUS mirror plate) or a metal roller (such as a SUS roller). Rather than directly pressing the resin sheet with the heat-pressing member, it is preferable to apply pressure through an elastic material such as heat-resistant rubber, so that the resin sheet fully conforms to the surface irregularities of the wiring layer.

[0124] The wiring layer and resin sheet can be laminated using a vacuum lamination method after removing the protective film from the resin sheet. The heat-pressing temperature for vacuum lamination is preferably between 60°C and 160°C, more preferably between 80°C and 140°C. The heat-pressing pressure is preferably between 0.098 MPa and 1.77 MPa, more preferably between 0.29 MPa and 1.47 MPa. The heat-pressing time is preferably between 20 seconds and 400 seconds, more preferably between 30 seconds and 300 seconds. Lamination is preferably performed under reduced pressure conditions of 13 hPa or less.

[0125] After lamination, the laminated resin sheet is smoothed under normal pressure (atmospheric pressure), for example, by applying pressure from the support side using a heated pressing member. The smoothing treatment can be performed under the same pressurizing conditions as those used for the lamination described above. Furthermore, lamination and smoothing can be performed continuously using a commercially available vacuum laminator.

[0126] After laminating the resin composition layer onto the wiring-embedded substrate, the resin composition layer can be thermally cured to form an insulating layer. For example, thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but typically the curing temperature is in the range of 120°C to 240°C, and the curing time is in the range of 5 minutes to 120 minutes. Prior to thermal curing, the resin composition layer can also be preheated at a temperature below the curing temperature.

[0127] The support of the resin sheet may be laminated on the substrate with the wiring layer and then peeled off after thermal curing. Alternatively, the support may be peeled off before laminating the resin sheet on the substrate with the wiring layer. Furthermore, the support may be peeled off before the roughening step described below.

[0128] After the resin composition layer is thermally cured to form the insulating layer, the surface of the insulating layer may be polished. The polishing method is not particularly limited and can be performed using a known method, such as using a flat grinding disc to polish the surface of the insulating layer.

[0129] <Step (3)> Step (3) is the step of forming connections between the wiring layers. Specifically, this involves forming via holes in the insulating layer to form a conductive layer, thereby forming connections between the wiring layers. Alternatively, this involves polishing or grinding the insulating layer to expose the wiring layer, thereby forming connections between the wiring layers. The conductive layer is sometimes referred to as the wiring layer.

[0130] When forming through-holes in the insulating layer to form the conductive layer and interconnect the wiring layers, the method for forming the through-holes is not particularly limited. Examples include laser irradiation, etching, and mechanical drilling, with laser irradiation being preferred. Laser irradiation can be performed using any laser processing machine, such as a carbon dioxide laser, a YAG laser, or an excimer laser. Specifically, laser irradiation is performed from the support side of the resin sheet to penetrate the support and the insulating layer, exposing the wiring layer and forming the through-holes.

[0131] The conditions for laser irradiation are not particularly limited, and laser irradiation can be carried out using any appropriate steps in accordance with conventional methods in conjunction with the selected means.

[0132] The shape of the through hole, when viewed from the extension direction, has no particular limitation on the shape of its opening outline, and is generally circular (slightly circular).

[0133] After forming the through-holes, a desmearing step is performed to remove contaminants from the through-holes. When forming the conductive layer using plating, as described later, the through-holes can be subjected to a wet desmearing process, for example. When forming the conductive layer using sputtering, a dry desmearing process, such as a plasma treatment process, can be performed. Furthermore, the desmearing process can also be combined with a roughening process.

[0134] Before forming the conductive layer, the vias and insulating layer may be roughened. This roughening process can be performed using a commonly used sequence and conditions. Examples of dry roughening include plasma treatment, while wet roughening includes a method that sequentially uses a swelling treatment using a swelling fluid, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing fluid.

[0135] The surface roughness (Ra) of the insulating layer after roughening treatment is preferably 350 nm or greater, more preferably 400 nm or greater, and particularly preferably 450 nm or greater. The upper limit is preferably 700 nm or less, more preferably 650 nm or less, and particularly preferably 600 nm or less. The surface roughness (Ra) can be measured, for example, using a non-contact surface roughness meter.

[0136] After the through-holes are formed, a conductor layer is formed. The conductor material constituting the conductor layer is not particularly limited. The conductor layer can be formed using any suitable method known in the art, such as plating, sputtering, and evaporation, and is preferably formed by plating. In a preferred embodiment, for example, a conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer using a known technique such as a semi-additive process or a fully additive process. Among these, the semi-additive process is preferred. In addition, when the support in the resin sheet is a metal foil, a known technique such as a subtractive process can be used to form a conductor layer having a desired wiring pattern. The conductor layer can be a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers formed of different types of metals or alloys are laminated.

[0137] Specifically, the plating method involves forming a plating seed layer on the surface of the insulating layer using electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer in accordance with the desired wiring pattern. An electroplating layer is then formed on the exposed plating seed layer via electroplating. During this process, a buried via (filled via) can also be formed simultaneously with the electroplating layer. After the electroplating layer is formed, the mask pattern is removed. Subsequently, the unnecessary plating seed layer is removed using etching or other methods, thereby forming a conductive layer having the desired wiring pattern. Furthermore, the dry film used to form the mask pattern during the formation of the conductive layer is the same as the dry film described above.

[0138] The conductor layer includes not only linear wiring but also electrode pads (land) for carrying external terminals, etc. In addition, the conductor layer may be composed only of electrode pads.

[0139] Furthermore, the conductor layer can be formed by forming an electrolytic plating layer and buried vias without using a mask pattern after forming a plating seed layer, and then performing patterning by etching.

[0140] When polishing or grinding the insulating layer to expose the wiring layer and establish connections between the wiring layers, the polishing or grinding method for the insulating layer is not particularly limited, as long as the wiring layer is exposed and the polished or ground surface is level. Conventional polishing or grinding methods can be used, such as chemical mechanical polishing using a chemical mechanical polishing device, mechanical polishing using a mirror surface, or flat grinding using rotating abrasive grains. The steps for forming vias in the insulating layer to form the conductive layer and establish connections between the wiring layers are similar, and can include a stain removal step, a roughening step, or the formation of a conductive layer. Furthermore, the entire wiring layer need not be exposed; only a portion may be exposed.

[0141] <Step (4)> Step (4) is the step of removing the substrate to form the circuit substrate of the present invention. The method for removing the substrate is not particularly limited. In a preferred embodiment, the circuit substrate is peeled off from the substrate at the interface between the first and second metal layers, and the second metal layer is then etched away using, for example, a copper chloride aqueous solution. If necessary, the substrate can also be peeled off while the conductive layer is protected by a protective film.

[0142] In other embodiments, the circuit substrate can also be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as when using a resin sheet.

[0143] [Semiconductor chip packaging] The first aspect of the semiconductor chip package of the present invention is a semiconductor chip package obtained by mounting a semiconductor chip on the above-mentioned circuit substrate. The semiconductor chip package can be obtained by connecting the above-mentioned circuit substrate to the semiconductor chip.

[0144] As long as the terminal electrodes of the semiconductor chip can form a conductive connection with the wiring of the circuit substrate, the connection conditions are not particularly limited, and known conditions used in flip-chip mounting of semiconductor chips can be used. Furthermore, the semiconductor chip and circuit substrate may be connected via an insulating adhesive.

[0145] In a preferred embodiment, the semiconductor wafer is pressed onto the circuit substrate. The pressing conditions include, for example, a pressing temperature in the range of 120°C to 240°C (preferably 130°C to 200°C, more preferably 140°C to 180°C) and a pressing time in the range of 1 second to 60 seconds (preferably 5 seconds to 30 seconds).

[0146] Another preferred embodiment is to reflow the semiconductor chip onto the circuit board for connection. The reflow conditions are, for example, in the range of 120°C to 300°C.

[0147] After the semiconductor chip is connected to the circuit substrate, for example, the semiconductor chip can be filled with an underfill material to produce a semiconductor chip package. The underfill material can be filled using known methods. The resin composition or resin sheet of the present invention can also be used as an underfill material.

[0148] A second aspect of the semiconductor chip package of the present invention is, for example, a semiconductor chip package (Fan-out WLP) as shown in one example of FIG1 . The semiconductor chip package (Fan-out WLP) 100 shown in one example of FIG1 is a semiconductor chip package using a sealing layer 120 made from the resin composition or resin sheet of the present invention. The semiconductor chip package 100 includes a sealing layer 120 formed to cover and surround a semiconductor chip 110, a redistribution layer (insulating layer) 130 on the side opposite to the sealing layer covering the semiconductor chip 110, a conductive layer (redistribution layer) 140, a solder resist layer 150, and bumps 160. The manufacturing method of these semiconductor chip packages includes: (A) Step of laminating a pre-fixed film on a substrate, (B) the step of pre-fixing the semiconductor wafer on the pre-fixing film, (C) laminating the resin composition layer of the resin sheet of the present invention on a semiconductor wafer, or coating the resin composition of the present invention on a semiconductor wafer and thermally curing it to form a sealing layer, (D) the step of peeling the substrate and the pre-fixed film from the semiconductor wafer, (E) a step of forming a redistribution layer (insulating layer) on the surface of the substrate and the pre-fixed film peeled off from the semiconductor wafer, (F) forming a conductor layer (rewiring layer) on the redistribution forming layer (insulating layer), and (G) forming a solder resist layer on the conductive layer. Furthermore, the method for manufacturing a semiconductor chip package also includes (H) cutting a plurality of semiconductor chip packages into individual semiconductor chip packages to form individual chips.

[0149] <Step (A)> Step (A) is a step of laminating a pre-fixed film onto a substrate. The lamination conditions for the substrate and the pre-fixed film are the same as those for laminating the wiring layer and the resin sheet in step (2) of the circuit board manufacturing method, and the preferred range is also the same.

[0150] The material used as the substrate is not particularly limited. Examples of the substrate include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); FR-4 substrates, which are glass fibers impregnated with epoxy resin and then heat-cured; BT resins, etc., which are bismaleimide-based substrates. Substrates formed of resin, etc.

[0151] The material of the pre-bonding film is not particularly limited as long as it can be peeled from the semiconductor wafer in step (D) described below and also pre-bond the semiconductor wafer. Commercially available pre-bonding films can be used, such as LIWA-α manufactured by Nitto Denko Corporation.

[0152] <Step (B)> Step (B) involves pre-mounting the semiconductor wafer on the pre-mounting film. Pre-mounting the semiconductor wafer can be performed using conventional equipment such as flip-chip connectors and die bonders. The arrangement and number of semiconductor wafers can be appropriately determined based on the shape and size of the pre-mounting film, the desired semiconductor package production volume, and other factors. For example, the wafers can be pre-mounted in a matrix of multiple rows and columns.

[0153] <Step (C)> Step (C) is a step of laminating the resin composition layer of the resin sheet of the present invention onto a semiconductor wafer, or coating the resin composition of the present invention onto a semiconductor wafer and thermally curing the resin composition to form a sealing layer. In step (C), it is preferred to laminate the resin composition layer of the resin sheet onto the semiconductor wafer and thermally cure the resin composition layer to form the sealing layer.

[0154] A method for laminating a semiconductor wafer and a resin sheet can be performed by, for example, applying heat and pressure to the resin sheet from the support side after removing the protective film from the resin sheet. The member for applying heat and pressure to the semiconductor wafer (hereinafter referred to as the "heat and pressure member") can be, for example, a heated metal plate (such as a SUS mirror plate) or a metal roller (such as a SUS roller). Rather than directly applying pressure to the resin sheet with the heat and pressure member, it is preferable to apply pressure through an elastic material such as heat-resistant rubber, so that the resin sheet fully conforms to the surface irregularities of the semiconductor wafer.

[0155] Furthermore, the method for laminating the semiconductor wafer and the resin sheet can be performed using a vacuum lamination method after removing the protective film from the resin sheet. The lamination conditions in the vacuum lamination method are the same as those for laminating the wiring layer and the resin sheet in step (2) of the method for manufacturing a circuit board, and the preferred range is also the same.

[0156] The support of the resin sheet can be peeled off after the resin sheet is laminated on the semiconductor chip and thermally cured, or the support can be peeled off before the resin sheet is laminated on the semiconductor chip.

[0157] The coating conditions of the resin composition are the same as those for forming the resin composition layer in the resin sheet of the present invention, and the preferred range is also the same.

[0158] <Step (D)> Step (D) involves peeling the substrate and pre-mounted film from the semiconductor wafer. The peeling method can be modified appropriately based on the material of the pre-mounted film. Examples include heating the pre-mounted film to allow it to foam (or expand) before peeling, and irradiating it with ultraviolet light from the substrate side to reduce the film's adhesive strength before peeling.

[0159] In methods where the pre-bonded film is heated to foam (or expand) before being peeled off, the heating conditions are typically between 100°C and 250°C for 1 to 90 seconds or 5 to 15 minutes. In methods where the pre-bonded film is irradiated with ultraviolet light from the substrate side to reduce its adhesion before peeling, the ultraviolet radiation dose is typically between 10 mJ / cm² and 1000 mJ / cm².

[0160] <Step (E)> Step (E) is a step of forming a redistribution layer (insulating layer) on the surface of the substrate and the pre-fixed film peeled off from the semiconductor wafer.

[0161] The material that can form the redistribution layer (insulating layer) is not particularly limited as long as it exhibits insulating properties when formed. However, from the perspective of ease of manufacturing semiconductor chip packages, photosensitive resins and thermosetting resins are preferred. The thermosetting resin can be a resin composition having the same composition as that used to form the resin sheet of the present invention.

[0162] After the redistribution forming layer (insulating layer) is formed, through holes can be formed in the redistribution forming layer (insulating layer) for the purpose of forming interlayer connections between the semiconductor wafer and the conductor layer described later.

[0163] When forming a through hole, if the material forming the redistribution forming layer (insulating layer) is a photosensitive resin, first, the surface of the redistribution forming layer (insulating layer) can be irradiated with active energy rays through a mask pattern to photoharden the redistribution layer in the irradiated portion.

[0164] Active energy rays include, for example, ultraviolet rays, visible light, electron beams, and X-rays, with ultraviolet rays being particularly preferred. The ultraviolet irradiation dose and irradiation time can be appropriately adjusted depending on the photosensitive resin. The exposure method can be either a contact exposure method, in which the mask pattern is closely attached to the redistribution formation layer (insulating layer), or a non-contact exposure method, in which parallel light is used to expose the mask pattern without closely attaching it to the redistribution formation layer (insulating layer).

[0165] Next, the redistribution layer (insulating layer) is developed to remove the unexposed areas, thereby forming vias. Development can be performed using either wet or dry methods. A known developer can be used for wet development.

[0166] The developing method includes, for example, immersion, stirring, spraying, brushing, and scraping. From the perspective of resolution, the stirring method is preferred.

[0167] When the material forming the redistribution layer (insulating layer) is a thermosetting resin, the method for forming the through-holes is not particularly limited. Examples include laser irradiation, etching, and mechanical drilling, with laser irradiation being preferred. Laser irradiation can be performed using any suitable laser processing machine, such as a carbon dioxide laser, UV-YAG laser, or excimer laser.

[0168] The conditions for laser irradiation are not particularly limited, and laser irradiation can be carried out using any appropriate steps in accordance with conventional methods in conjunction with the selected means.

[0169] The shape of the through-hole opening outline, when viewed in the extension direction, is not particularly limited and is generally circular (slightly circular). The top diameter of the through-hole (the diameter of the opening at the surface of the redistribution layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit is not particularly limited, but is generally preferably 10 μm or more, more preferably 15 μm or more, and particularly preferably 20 μm or more.

[0170] <Step (F)> Step (F) is the step of forming a conductor layer (rewiring layer) on the redistribution formation layer (insulating layer). The method for forming the conductor layer on the redistribution formation layer (insulating layer) is the same as the method for forming the conductor layer after forming through holes in the insulating layer in step (3) in the circuit board manufacturing method, and the preferred range is also the same. Alternatively, steps (E) and (F) may be repeated to form an alternating stack of the conductor layer (rewiring layer) and the redistribution formation layer (insulating layer).

[0171] <Step (G)> Step (G) is a step of forming a solder resist layer on the conductor layer.

[0172] The material used to form the solder resist layer is not particularly limited, as long as it provides insulating properties during formation. From the perspective of ease of manufacturing semiconductor chip packages, photosensitive resins and thermosetting resins are preferred. The thermosetting resin can be a resin composition having the same composition as that used to form the resin sheet of the present invention.

[0173] Furthermore, in step (G), bumping can be performed to form bumps, if necessary. Bumping can be performed using known methods such as solder balls and solder plating. Furthermore, during the bumping process, through-hole formation can be performed using the same method as in step (E).

[0174] <Step (H)> The method for manufacturing a semiconductor chip package may include a step (H) in addition to steps (A) to (G). Step (H) is a step of cutting a plurality of semiconductor chip packages into individual semiconductor chip packages to form singulated chips.

[0175] The method for cutting the semiconductor chip package into individual semiconductor chip packages is not particularly limited, and a known method can be used.

[0176] The third aspect of the semiconductor chip package of the present invention is, for example, the redistribution layer (insulating layer) 130 and the solder resist layer 150 in the semiconductor chip package (Fan-out type WLP) shown in one example of FIG. 1 , which is a semiconductor chip package made using the resin composition or resin sheet of the present invention.

[0177] [Semiconductor devices] Semiconductor devices incorporating the semiconductor chip package of the present invention can be exemplified by various semiconductor devices that can be used in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0178] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following descriptions, "parts" and "%" representing "amounts" are, unless otherwise specified, intended to represent "parts by mass" and "% by mass," respectively.

[0179] <Preparation of Samples for Peel Strength Measurement> (1) Bottom layer processing of inner circuit substrate Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.3mm, R5715ES manufactured by Panasonic) with inner layer circuits were immersed in CZ8100 manufactured by Merck to roughen the copper surface.

[0180] (2) Lamination of resin sheets The resin sheets produced in the Examples and Comparative Examples were laminated onto both sides of the inner circuit board using a batch vacuum press laminator (Nikko Metal Co., Ltd., two-step stack laminator "CVP700"), with the resin composition layer attached to the inner circuit board. Lamination was performed by reducing the pressure to below 13 hPa for 30 seconds, followed by pressing at 100°C and 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100°C and 0.5 MPa for 60 seconds. The resulting laminated sheet with the resin composition layer was heat-treated at 180°C for 30 minutes to cure the resin composition layer, producing a cured laminated sheet.

[0181] (3) Roughening treatment The resulting laminate with the cured product was immersed in "Swelling Dip Securiganth P" (swelling solution) containing diethylene glycol monobutyl ether (made by ATOTETCH, Japan) at 60°C for 5 minutes. It was then immersed in "Concentrate Compact P" (an aqueous solution of 60 g / L KMnO₄ and 40 g / L NaOH, an oxidizing agent (roughening solution)) (made by ATOTETCH, Japan) at 80°C for 10 minutes. Finally, it was immersed in "Reduction Solution Security Gant P" (neutralizing solution) (made by ATOTETCH, Japan) at 40°C for 5 minutes to roughen the surface of the cured product. The roughened laminate was used as evaluation substrate A.

[0182] (4) Metal layer formed by plating Evaluation substrate A was immersed in an electroless plating solution containing PdCl₂, followed by an electroless copper plating solution. Next, copper sulfate electrolytic plating was performed to form a 30μm thick metal layer on the roughened surface of the cured product. Next, annealing was performed at 180°C for 60 minutes. The resulting laminate was designated evaluation substrate B.

[0183] <Determination and Evaluation of the Tensile Peel Strength (Peel Strength) of the Metal Layer> A 10 mm wide and 100 mm long section was cut into the metal layer of evaluation substrate B. One end of the section was peeled off and clamped using a fixture (AUTOCOM AC-50C-SL, manufactured by DSE). The peel strength was determined by measuring the load (kgf / cm) at room temperature when the section was pulled vertically and peeled off 20 mm at a speed of 50 mm / min.

[0184] <Preparation of Cured Material for Elastic Modulus Evaluation> A release PET film (501010, manufactured by Lindex, 38 μm thick, 240 mm square) was placed on a glass cloth-based epoxy resin double-sided copper-clad laminate (R5715ES, 0.7 mm thick, 255 mm square) by attaching its untreated side to the laminate. The release PET film was secured on all four sides with polyimide adhesive tape (10 mm wide).

[0185] The resin sheets (167 x 107 mm square) produced in the Examples and Comparative Examples were laminated in the center using a batch vacuum press laminator (CVP700, a two-stage stack laminator manufactured by Nikko Metal Co., Ltd.), with the release surface of the release PET film attached to the resin composition layer. Lamination was performed by depressurizing the film to below 13 hPa for 30 seconds, followed by pressing at 100°C and 0.74 MPa for 30 seconds.

[0186] Next, the support is peeled off, and the resin composition layer is thermally cured under curing conditions of 180° C. for 90 minutes.

[0187] After thermal curing, the polyimide adhesive tape was peeled off, separating the resin composition layer from the glass cloth-based epoxy resin double-sided copper laminate. The release PET film was then peeled off from the resin composition layer to produce a thin sheet of cured product (for evaluation).

[0188] <Determination of elastic modulus> The hardened material for evaluation was cut into dumbbell-shaped No. 1 test pieces to prepare them. The tensile strength of these test pieces was measured using an Orientec RTC-1250A tensile testing machine, and the modulus of elasticity at 23°C was determined. The measurement method was based on JIS K7127. This procedure was repeated three times, and the average values ​​are shown in the table.

[0189] <Warp Amount Evaluation> The resin sheets produced in the Examples and Comparative Examples were laminated onto one side of a glass cloth-based BT resin double-sided copper-clad laminate (15 cm x 18 cm, copper foil thickness 18 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Co., Ltd., HL832NSF LCA) using a batch vacuum press laminator (Nikko Metal Co., Ltd., two-stage stack laminator "CVP700"). After removing the PET release liner, the sheets were heat-cured at 100°C for 30 minutes and then at 180°C for 30 minutes. The sheets were then placed on a flat surface to measure their warpage. The average warpage at each of the four corners was marked as less than 1 cm, 1-2 cm as "△," and 2 cm or more as "×."

[0190] <Determination of Thermal Conductivity of Cured Material> (1) Preparation of hardened sample The resin coatings prepared in the Examples and Comparative Examples were applied using a slot coater onto a PET film ("LUMMIOR R80" manufactured by Toray Industries, Inc., 38 μm thick, softening point 130°C) that had been release-treated with an alkyd resin release agent ("AL-5" manufactured by Lindex Corporation) to a thickness of 100 μm after drying. The film was then dried at 80°C to 100°C (average 90°C) for 7 minutes to form a resin composition layer.

[0191] Three layers of the resin composition were repeatedly stacked using a batch vacuum pressure laminator (Nikko Metal Co., Ltd., two-step stack laminator "CVP700"), followed by lamination. The resin composition layers were cured at 180°C for 90 minutes to produce a cured sample. Lamination was performed by reducing the pressure to below 13 hPa over 30 seconds, followed by pressing at 100°C and 0.4 MPa for 20 seconds.

[0192] (2) Determination of thermal diffusivity α The thermal diffusivity α (m² / s) of the cured sample in the thickness direction was measured using the ai-Phase Mobile 1u (manufactured by ai-Phase). Three measurements were performed on the same sample, and the average value was calculated.

[0193] (3) Determination of specific heat capacity Cp The cured sample was heated from -40°C to 80°C at a rate of 10°C / min using a differential scanning calorimeter (DSC7020, manufactured by SII Nanotech). The specific heat capacity (Cp) (J / kg·K) of the cured sample at 25°C was calculated based on the measurement results.

[0194] (4) Determination of density ρ The density (kg / m3) of the cured sample was measured using an analytical balance XP105 manufactured by Mettler Toledo (using a specific gravity measurement kit).

[0195] (5) Calculation of thermal conductivity λ Substitute the thermal diffusivity α (m 2 / s), specific heat capacity Cp (J / kg·K), and density ρ (kg / m 3) obtained from (2) to (4) above into the following formula (I) to calculate the thermal conductivity λ (W / m·K). λ=α×Cp×ρ (I)

[0196] <Determination of Melt Viscosity> The melt viscosity of the resin composition layer in the resin sheets produced in the Examples and Comparative Examples was measured using a Rheosol-G3000 (UBM) with a resin weight of 1g and an 18mm diameter parallel plate. The melt viscosity was measured from a starting temperature of 60°C to 200°C at a heating rate of 5°C / min, a measurement temperature interval of 2.5°C, and an oscillation of 1 Hz / deg.

[0197] <Synthesis Example 1: Synthesis of Polymer Compound 1> In a reaction vessel, 69 g of G-3000 (difunctional hydroxyl-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g / eq., solids 100% by mass; manufactured by Nippon Soda Co., Ltd.), 40 g of IPUZOURU 150 (aromatic hydrocarbon mixed solvent; manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin dilaurate were uniformly mixed and dissolved. After achieving a homogeneous state, the temperature was raised to 50°C. Then, 8 g of isophorone diisocyanate (manufactured by Evonik Degussa Japan, IPDI, isocyanate equivalent = 113 g / eq.) was added while stirring, and the reaction was allowed to proceed for approximately 3 hours. Next, the reaction mixture was cooled to room temperature. 23 g of cresol-novolac resin (KA-1160, manufactured by DIC Corporation, hydroxyl equivalent = 117 g / eq.) and 60 g of ethyl diglycol acetate (manufactured by DAICEL) were added to the mixture. The mixture was heated to 80°C with stirring and allowed to react for approximately 4 hours. FT-IR was used to confirm the disappearance of the NCO peak at 2250 cm⁻¹. The reaction was considered terminated when the NCO peak disappeared. After cooling to room temperature, the mixture was filtered through a 100 μm filter cloth to yield Polymer Compound 1 (50% by mass), which has a polybutadiene structure and phenolic hydroxyl groups.

[0198] <Synthesis Example 2: Synthesis of Polymer Compound 2> In a reaction vessel, 80 g of polycarbonate diol (number average molecular weight: approximately 1,000, hydroxyl equivalent: 500, nonvolatile content: 100%) and 0.01 g of dibutyltin dilaurate were uniformly dissolved in 37.6 g of diethylene glycol monoethyl ether acetate ("Ethyl diethylene glycol acetate" manufactured by Daicel) Next, the mixture was heated to 50°C, and 27.8 g of toluene-2,4-diisocyanate (isocyanate equivalent: 87.08) was added while stirring. The reaction was allowed to proceed for approximately 3 hours. Next, the reaction mixture was cooled to room temperature. 14.3 g of benzophenonetetracarboxylic dianhydride (anhydride equivalent: 161.1), 0.12 g of triethylenediamine, and 84.0 g of diethylene glycol monoethyl ether acetate ("Ethyl diethylene glycol acetate" manufactured by DAICEL) were added to the mixture. The mixture was heated to 130°C with stirring and allowed to react for approximately 4 hours. FT-IR was used to confirm the disappearance of the NCO peak at 2250 cm⁻¹. The reaction was considered terminated when the NCO peak disappeared. The reaction mixture was cooled to room temperature and filtered through a 100 μm filter cloth to yield Polymer Compound 2 (50% by mass non-volatile content) with a carbonate structure.

[0199] <Measurement of Average Particle Size of Thermally Conductive Filler> To a 20ml vial, add 0.01g of thermally conductive filler, 0.2g of a nonionic dispersant ("T208.5" manufactured by NOF Corporation), and 10g of pure water. Ultrasonic dispersion was performed for 10 minutes using an ultrasonic cleaner to prepare a sample. Next, the sample was placed in a laser diffraction particle size distribution analyzer ("SALD2200" manufactured by Shimadzu Corporation) and irradiated with ultrasound for 10 minutes in a circulating state. The ultrasound was then stopped, and the sample was allowed to continue circulating for a particle size distribution measurement to determine the average particle size of the thermally conductive filler. The refractive index during the measurement was set to 1.45-0.001i.

[0200] <Measurement of Specific Surface Area of ​​Thermally Conductive Filler> The specific surface area was determined by the nitrogen BET method using an automatic specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH).

[0201] <Thermal conductive filler used> Alumina 1: A mixture of aluminas with different average particle sizes and specific surface areas, with an average particle size of 3 μm and a specific surface area of ​​1.5 m² / g, surface-treated with KBM573 (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Alumina 2: A mixture of aluminas with different average particle sizes and specific surface areas, with an average particle size of 3 μm and a specific surface area of ​​1.5 m² / g, surface-treated with KBM5783 (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Alumina 3: A mixture of aluminas with different average particle sizes and specific surface areas, with an average particle size of 3 μm and a specific surface area of ​​1.5 m 2 / g, surface treated with "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Alumina 4: A mixture of aluminas with different average particle sizes and specific surface areas, with an average particle size of 3 μm and a specific surface area of ​​1.5 m² / g, surface-treated with KBM903 (3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0202] <Example 1> 6 parts of aminophenol type epoxy resin (Mitsubishi Chemical Corporation "630", epoxy equivalent: 95 g / eq), 5 parts of liquid epoxy resin (Nippon Steel & Sumitomo Metal Chemical Corporation "ZX1059", a 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 2 parts of biphenyl type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy equivalent: 185 g / eq), and 2 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258 g / eq) were dissolved in 10 parts of methyl ethyl ketone, and then 1 part of aluminum oxide was mixed. 270 parts of alumina, 24 parts of a polymer compound 1 (50% solids by mass, number average molecular weight 5500), 3 parts of an active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation, active ester equivalent 223 g / eq, 65% solids solution in toluene), 2 parts of a solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Corporation, hydroxyl equivalent 215 g / eq, 50% solids solution in methyl ethyl ketone), 1 part of a hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), 10% solids solution in MEK), and 15 parts of methyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to prepare a resin coating 1.

[0203] Resin coating 1 was coated using a slot coater onto a PET film ("LUMMIOR R80" manufactured by Toray Industries, Inc., 38 μm thick, softening point 130°C, also referred to as "release PET") that had been release-treated with an alkyd resin release agent ("AL-5" manufactured by Lindex Corporation). The film was then dried at 80°C to 100°C (average 90°C) for 5 minutes to produce a resin sheet 1.

[0204] <Example 2> 6 parts of aminophenol type epoxy resin (Mitsubishi Chemical Corporation "630", epoxy equivalent: 95 g / eq), 5 parts of liquid epoxy resin (Nippon Steel & Sumitomo Metal Chemical Corporation "ZX1059", a 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 2 parts of biphenyl type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy equivalent: 185 g / eq), and 2 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258 g / eq) were dissolved in 10 parts of methyl ethyl ketone, and then 1 part of aluminum oxide was mixed. 270 parts, 24 parts of polymer compound 1 (50% solids by mass, number average molecular weight 5500), 6 parts of an active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation, active ester equivalent 223 g / eq, 65% solids solution in toluene), 6 parts of a solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Corporation, hydroxyl equivalent 215 g / eq, used as a 50% solids solution in methyl ethyl ketone), 1 part of a hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), 10% solids solution in MEK), and 15 parts of methyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to prepare resin coating 2. In Example 1, resin sheet 2 was prepared by the same method as in Example 1, except that resin coating 1 was replaced with resin coating 2.

[0205] <Example 3> 6 parts of aminophenol type epoxy resin (Mitsubishi Chemical Corporation "630", epoxy equivalent: 95 g / eq), 5 parts of liquid epoxy resin (Nippon Steel & Sumitomo Metal Chemical Corporation "ZX1059", a 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 2 parts of biphenyl type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy equivalent: 185 g / eq), and 2 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258 g / eq) were dissolved in 10 parts of methyl ethyl ketone, and then 1 part of aluminum oxide was mixed. 240 parts, 24 parts of polymer compound 1 (50% solids by mass, number average molecular weight 5500), 3 parts of an active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation, active ester equivalent 223 g / eq, 65% solids solution in toluene), 2 parts of a solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Corporation, hydroxyl equivalent 215 g / eq, used as a 50% solids solution in methyl ethyl ketone), 1 part of a hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), 10% solids solution in MEK), and 15 parts of methyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to prepare resin coating 3. Resin sheet 3 was prepared by the same method as in Example 1, except that resin coating 1 was replaced with resin coating 3.

[0206] <Example 4> 6 parts of aminophenol type epoxy resin (Mitsubishi Chemical Corporation's "630", epoxy equivalent: 95 g / eq), 5 parts of liquid epoxy resin (Nippon Steel & Sumitomo Metal Chemical Corporation's "ZX1059", a 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 2 parts of biphenyl type epoxy resin (Mitsubishi Chemical Corporation's "YX4000H", epoxy equivalent: 185 g / eq), and 2 parts of biphenyl type epoxy resin (Nippon Kayaku Corporation's "NC3100", epoxy equivalent: 258 g / eq) were dissolved in 10 parts of methyl ethyl ketone, and then mixed with aluminum oxide 2 parts. 270 parts, 24 parts of polymer compound 1 (50% solids by mass, number average molecular weight 5500), 3 parts of an active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation, active ester equivalent 223 g / eq, 65% solids solution in toluene), 2 parts of a solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Corporation, hydroxyl equivalent 215 g / eq, used as a 50% solids solution in methyl ethyl ketone), 1 part of a hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), 10% solids solution in MEK), and 15 parts of methyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to prepare resin coating 4. In Example 1, resin sheet 4 was prepared by the same method as in Example 1, except that resin coating 1 was replaced with resin coating 4.

[0207] <Example 5> 6 parts of aminophenol type epoxy resin (Mitsubishi Chemical Corporation "630", epoxy equivalent: 95 g / eq), 5 parts of liquid epoxy resin (Nippon Steel & Sumitomo Metal Chemical Corporation "ZX1059", a 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 2 parts of biphenyl type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy equivalent: 185 g / eq), and 2 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258 g / eq) were dissolved in 10 parts of methyl ethyl ketone, and then 1 part of aluminum oxide was mixed. 270 parts, 24 parts of polymer compound 2 (50% solids by mass, number average molecular weight 6000), 3 parts of an active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation, active ester equivalent 223 g / eq, 65% solids solution in toluene), 2 parts of a solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Corporation, hydroxyl equivalent 215 g / eq, used as a 50% solids solution in methyl ethyl ketone), 1 part of a hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), 10% solids solution in MEK), and 15 parts of methyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to prepare resin coating 5. In Example 1, resin sheet 5 was prepared by the same method as in Example 1, except that resin coating 1 was replaced with resin coating 5.

[0208] <Comparative Example 1> 6 parts of aminophenol type epoxy resin (Mitsubishi Chemical Corporation "630", epoxy equivalent: 95 g / eq), 5 parts of liquid epoxy resin (Nippon Steel & Sumitomo Metal Chemical Corporation "ZX1059", a 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 2 parts of biphenyl type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy equivalent: 185 g / eq), and 2 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258 g / eq) were dissolved in 10 parts of methyl ethyl ketone, and then 1 part of aluminum oxide was mixed. 270 parts, 24 parts of polymer compound 1 (50% solids by mass, number average molecular weight 5500), 6 parts of a solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 215 g / eq, used as a 50% solids solution in methyl ethyl ketone), 1 part of a hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), a 10% solids solution in MEK), and 15 parts of methyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to produce resin coating 6. In Example 1, resin sheet 6 was produced by the same method as in Example 1, except that resin coating 1 was replaced with resin coating 6.

[0209] <Comparative Example 2> 6 parts of aminophenol type epoxy resin (Mitsubishi Chemical Corporation "630", epoxy equivalent: 95 g / eq), 5 parts of liquid epoxy resin (Nippon Steel & Sumitomo Metal Chemical Corporation "ZX1059", a 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 2 parts of biphenyl type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy equivalent: 185 g / eq), and 2 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258 g / eq) were dissolved in 10 parts of methyl ethyl ketone, and then 1 part of aluminum oxide was mixed. 270 parts, 26 parts of polymer compound 1 (50% solids by mass, number average molecular weight 5500), 2 parts of a solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 215 g / eq, used as a 50% solids solution in methyl ethyl ketone), 2 parts of a hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), a 10% solids solution in MEK) 1 part, and 15 parts of methyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to produce resin coating 7. Resin sheet 7 was produced by the same method as in Example 1, except that resin coating 1 was replaced with resin coating 7.

[0210] <Comparative Example 3> 6 parts of aminophenol type epoxy resin (Mitsubishi Chemical Corporation's "630", epoxy equivalent: 95 g / eq), 5 parts of liquid epoxy resin (Nippon Steel & Sumitomo Metal Chemical Corporation's "ZX1059", a 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 2 parts of biphenyl type epoxy resin (Mitsubishi Chemical Corporation's "YX4000H", epoxy equivalent: 185 g / eq), and 2 parts of biphenyl type epoxy resin (Nippon Kayaku Corporation's "NC3100", epoxy equivalent: 258 g / eq) were dissolved in 10 parts of methyl ethyl ketone, and then 3 parts of aluminum oxide were mixed. 270 parts, 24 parts of polymer compound 1 (50% solids by mass, number average molecular weight 5500), 6 parts of a solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 215 g / eq, used as a 50% solids solution in methyl ethyl ketone), 1 part of a hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), a 10% solids solution in MEK), and 15 parts of methyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to produce resin coating 8. Resin sheet 8 was produced by the same method as in Example 1, except that resin coating 1 was replaced with resin coating 8.

[0211] <Comparative Example 4> 6 parts of aminophenol type epoxy resin (Mitsubishi Chemical Corporation's "630", epoxy equivalent: 95 g / eq), 5 parts of liquid epoxy resin (Nippon Steel & Sumitomo Metal Chemical Corporation's "ZX1059", a 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq), 2 parts of biphenyl type epoxy resin (Mitsubishi Chemical Corporation's "YX4000H", epoxy equivalent: 185 g / eq), and 2 parts of biphenyl type epoxy resin (Nippon Kayaku Corporation's "NC3100", epoxy equivalent: 258 g / eq) were dissolved in 10 parts of methyl ethyl ketone, and then 4 parts of aluminum oxide were mixed. 270 parts, 24 parts of polymer compound 1 (50% solids by mass, number average molecular weight 5500), 6 parts of a solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 215 g / eq, used as a 50% solids solution in methyl ethyl ketone), 1 part of a hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), a 10% solids solution in MEK), and 15 parts of methyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to produce resin coating 9. Resin sheet 9 was produced by the same method as in Example 1, except that resin coating 1 was replaced with resin coating 9.

[0212] The contents of the following table are as follows. Content of component (A): The content when the non-volatile content of the resin component after removing component (C) is set to 100% by mass (C) Component content: The content when the non-volatile component of the resin composition is set to 100% by mass

[0213]

[0214] As shown in Examples 1-5, the insulating layers formed from the resin compositions containing components (A) to (D) exhibited excellent peel strength. On the other hand, Comparative Examples 1-4, which did not contain component (D), exhibited inferior peel strength compared to Examples 1-5. Furthermore, Comparative Examples 3-4, in which component (C) was not treated with N-phenyl-3-aminoalkyltrimethoxysilane, exhibited poor lamination properties and inferior peel strength due to excessively high melt viscosity. Furthermore, it was found that even when the components (E) and (F) were not contained in Examples 1 to 5, the results obtained were the same as those of the above-mentioned Examples, even though the difference in degree was not significant.

[0215] 100:Semiconductor chip packaging 110:Semiconductor wafer 120: Sealing layer 130: Rewiring forming layer (insulating layer) 140: Conductor layer (rewiring layer) 150:Solder resist layer 160: convex point

Claims

1. A resin composition, characterized by comprising: (A) a polymer compound having one or more structures selected from polybutadiene, polysiloxane, poly(meth)acrylate, polyalkylene, polyalkylene oxide, polyisoprene, polyisobutylene, and polycarbonate; (B) an epoxy resin; (C) a thermally conductive filler; and (D) an active ester curing agent, wherein... (A) Component has a functional group that can react with (B) Component; (C) Component contains aluminum oxide that has been surface-treated with an aminosilane coupling agent containing N-phenyl-3-aminopropyltrimethoxysilane; (D) Component content is 0.1% to 5% by mass when the non-volatile components in the resin composition are set to 100% by mass.

2. A resin composition having an elastic modulus of 11 GPa to 20 GPa after heat curing at 180°C for 90 minutes, characterized by comprising: (A) a polymer compound having one or more structures selected from polybutadiene, polysiloxane, poly(meth)acrylate, polyalkylene, polyalkylene oxide, polyisoprene, polyisobutylene, and polycarbonate; (B) an epoxy resin; (C) a thermally conductive filler; and (D) an active ester curing agent, wherein... (A) Component has a functional group that can react with (B) Component, and (C) Component contains aluminum oxide that has been surface-treated with an aminosilane coupling agent containing N-phenyl-3-aminopropyltrimethoxysilane.

3. A resin composition, characterized by comprising: (A) one or more polymeric compounds selected from a resin having a number average molecular weight (Mn) of 1,000 to 1,000,000 and a glass transition temperature of 25°C or below, and a resin that is liquid at 25°C; (B) an epoxy resin; (C) a thermally conductive filler; and (D) an active ester curing agent, wherein... (A) Component has a functional group that can react with (B) Component; (C) Component contains aluminum oxide that has been surface-treated with an aminosilane coupling agent containing N-phenyl-3-aminopropyltrimethoxysilane; (D) Component content is 0.1% to 5% by mass when the non-volatile components in the resin composition are set to 100% by mass.

4. A resin composition, characterized by comprising: (A) a polymer compound having one or more structures selected from polybutadiene, polysiloxane, poly(meth)acrylate, polyalkylene, polyalkylene oxide, polyisoprene, polyisobutylene, and polycarbonate; (B) an epoxy resin; (C) a thermally conductive filler; and (D) an active ester curing agent, wherein... (A) is one or more of the following: a resin with a number average molecular weight (Mn) of 1,000 to 1,000,000, or a resin with a glass transition temperature (Tg) of 25°C or less, and a resin that is liquid at 25°C; (A) has a functional group that can react with (B); and (A) has a content of 25% to 39.9% by mass when the resin content is set to 100% by mass. (C) contains alumina that has been surface-treated with an aminosilane coupling agent containing N-phenyl-3-aminopropyltrimethoxysilane.

5. A resin composition, characterized by comprising: (A) a polymer compound having one or more structures selected from polybutadiene, polysiloxane, poly(meth)acrylate, polyalkylene, polyalkylene oxide, polyisoprene, polyisobutylene, and polycarbonate; (B) an epoxy resin; (C) a thermally conductive filler; and (D) an active ester curing agent, wherein... (A) Component is one or more of the following: a resin with a number average molecular weight (Mn) of 1,000 to 1,000,000, or a resin selected from those with a glass transition temperature (Tg) of 25°C or less and those that are liquid at 25°C; (A) Component has a functional group that can react with (B) Component; (A) Component has a content of 10% to 65% by mass when the resin component is set as 100% by mass; (B) Component is a mixture of liquid epoxy resin and solid epoxy resin, and the mass ratio of liquid epoxy resin to solid epoxy resin (solid epoxy resin: liquid epoxy resin) is 1:0.3 to 1:10 by mass; (C) Component contains alumina surface-treated with an aminosilane coupling agent containing N-phenyl-3-aminopropyltrimethoxysilane.

6. The resin composition as claimed in claim 1 or 2, wherein, (A) The composition is one or more selected from resins with a glass transition temperature of 25°C or below and resins that are liquid at 25°C.

7. The resin composition of any one of claims 1 to 5, wherein, The hardened material formed by thermosetting the resin composition at 180°C for 30 minutes and then at 180°C for 60 minutes has a peel strength of 0.4 kgf / cm or higher from the metal layer formed by plating.

8. The resin composition of any one of claims 1 to 5, wherein, (C) The content of the component is 85% or more when the non-volatile component in the resin composition is 100% by mass.

9. The resin composition of any one of claims 1 to 5, wherein, The thermal conductivity of the cured material formed by heat curing the resin composition at 180°C for 90 minutes is above 1.5 W / m·K and below 5.0 W / m·K.

10. The resin composition of any one of claims 1 to 5, wherein, (A) The ingredient has one or more functional groups selected from hydroxyl, acid anhydride, phenolic hydroxyl, epoxy, isocyanate and carbamate groups.

11. The resin composition of any one of claims 1 to 5, wherein, (A) Component has a aceimine structure.

12. The resin composition of any one of claims 1 to 5, wherein, (A) Component has phenolic hydroxyl groups.

13. The resin composition of any one of claims 1 to 5, wherein, (A) Component has a polybutadiene structure and phenolic hydroxyl groups.

14. The resin composition of any one of claims 1 to 5 is a resin composition for the insulating layer of a semiconductor wafer package.

15. The resin composition of any one of claims 1 to 5 is a resin composition for the insulating layer of a circuit board formed by a semi-additive process.

16. A resin sheet, characterized in that it comprises: a support, and a resin composition layer comprising any one of claims 1 to 15 disposed on the support.

17. A circuit board, characterized in that it comprises: an insulating layer formed by curing a resin composition of any one of claims 1 to 15.

18. A semiconductor wafer package, characterized in that it comprises: a circuit substrate of claim 17, and a semiconductor wafer mounted on the aforementioned circuit substrate.

19. A semiconductor wafer package, characterized in that it comprises: a resin composition of any one of claims 1 to 15, or a semiconductor wafer sealed by a resin sheet of claim 16.

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