TWI835277B - resin composition - Google Patents

Abstract

[Problem] To provide a resin composition that can produce an insulating layer with excellent thermal conductivity and excellent peel strength to a metal layer, a resin sheet, a circuit substrate, and a semiconductor chip package using the resin composition. [Solution] A resin composition containing (A) having a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, and a polyalkylene oxide structure in the molecule , polymer compounds of more than one structure selected from polyisoprene structure, polyisobutylene structure, and polycarbonate structure, (B) epoxy resin, (C) thermally conductive filler, and (D) active ester Hardener.

Description

resin composition

The present invention relates to a resin composition. Also, related to resin sheets, circuit substrates, and semiconductor chip packages using resin compositions.

In recent years, as electronic devices have become smaller and more functional, the mounting density of semiconductor elements in printed wiring boards has tended to increase. As the functionality of mounted semiconductor elements becomes higher, a technology that can efficiently diffuse the heat generated by the semiconductor elements is also required. When the resin composition containing the thermally conductive filler is hardened to form an insulating layer, the thermal conductivity of the resulting insulating layer can be increased by increasing the content of the thermally conductive filler in the resin composition. However, the content of the thermally conductive filler is increased to When sufficient thermal conductivity is achieved, the adhesion strength of the resulting insulating layer to the metal layer on which wiring is to be formed tends to deteriorate.

For example, Patent Document 1 discloses a printed wiring board using a resin composition containing aluminum nitride or silicon nitride that is cured to form an insulating layer. In addition to generating thermal diffusivity, the printed wiring board has low surface roughness. The adhesion strength (peel strength) of the conductor layer allows good heat diffusion, etc. [Prior technical literature] [Patent Document]

[Patent Document 1] International Publication No. 2014/208352

[Problem to be solved by the invention]

In recent years, with the miniaturization and high functionality of electronic devices, in the process of thinning and shellless substrates, in addition to thermal diffusivity and adhesion strength (peel strength), a material is also being sought. It can suppress the warpage phenomenon that occurs when forming the insulating layer. There is a trade-off between these properties, so it is very difficult to design a balanced resin.

The present invention was conceived in view of solving the above-mentioned problems, and provides a product that can achieve a balance between excellent thermal conductivity, excellent peel strength for metal layers, and suppression of the amount of warpage that occurs when forming an insulating layer. Cured resin composition; resin sheets, circuit substrates, and semiconductor chip packages using the resin composition. [Methods to solve problems]

The inventors of the present invention have discovered that: (A) a molecule composed of a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkylene oxide structure, and a polyisoprene structure is found in the molecule; Composition of a polymer compound with one or more structures selected from diene structure, polyisobutylene structure, and polycarbonate structure, (B) epoxy resin, (C) thermally conductive filler, and (D) active ester hardener When the material is used, it is possible to obtain a product that has excellent thermal conductivity, excellent peeling strength for metal layers (especially metal layers formed by plating), and has excellent effects in suppressing warpage that occurs when forming an insulating layer. insulation layer, thus completing the present invention.

That is, the present invention includes the following contents. [1] A resin composition characterized by containing: (A) The molecule has a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkylene oxide structure, a polyisoprene structure, and a polyisobutylene structure, and polymer compounds with one or more structures selected from the polycarbonate structure, (B)Epoxy resin, (C) thermally conductive filler, and (D) Active ester hardener. [2] The resin composition as described in [1], wherein the resin composition is thermally hardened at 180°C for 30 minutes and then at 180°C for 60 minutes to form a hardened product, and the metal layer formed by plating The peel strength is above 0.4kgf/cm. [3] The resin composition according to [1] or [2], wherein the content of component (C) is 85% by mass or more when the non-volatile content in the resin composition is 100% by mass. [4] The resin composition according to any one of [1] to [3], wherein the component (C) contains alumina. [5] The resin composition according to any one of [1] to [4], wherein the component (C) is surface-treated with an aminosilane coupling agent. [6] The resin composition according to any one of [1] to [5], wherein component (C) is surface-treated with N-phenyl-3-aminoalkyltrimethoxysilane. [7] The resin composition according to 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 1.5W/m・K or above, 5.0W/m・K or less. [8] The resin composition according to any one of [1] to [7], wherein component (A) is selected from a resin with a glass transition temperature of 25°C or less and a resin that is liquid at 25°C. 1 or more of them. [9] The resin composition according to any one of [1] to [8], wherein component (A) has a functional group that can react with component (B). [10] The resin composition according to any one of [1] to [9], wherein component (A) has a hydroxyl group, an anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. One or more functional groups selected from the ester group. [11] The resin composition according to any one of [1] to [10], wherein component (A) has an amide imine structure. [12] The resin composition according to any one of [1] to [11], wherein component (A) has a phenolic hydroxyl group. [13] The resin composition according to any one of [1] to [12], wherein component (A) has a polybutadiene structure and has a phenolic hydroxyl group. [14] The resin composition according to any one of [1] to [13], which is a resin composition for an insulating layer of a semiconductor chip package. [15] The resin composition according to any one of [1] to [14], which is a resin composition for the insulating layer of a circuit substrate formed using a semi-additive process. [16] A resin sheet characterized by having a support body, and a resin composition layer provided on the support body and including the resin composition described in any one of [1] to [15]. [17] A circuit board characterized by including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [15]. [18] A semiconductor chip package, characterized by comprising: the circuit substrate described in [17], and a semiconductor chip mounted on the circuit substrate. [19] A semiconductor chip package, characterized by comprising: a semiconductor chip sealed with the resin composition described in any one of [1] to [15], or with the resin sheet described in [16]. [Effects of the invention]

According to the present invention, there is provided a method that can form a metal layer having excellent thermal conductivity and excellent adhesion strength to a metal layer, especially a metal layer formed by plating, while suppressing the amount of warpage generated when forming an insulating layer. A resin composition that can achieve a balanced hardened product; resin sheets, circuit substrates, and semiconductor chip packages using the resin composition.

Hereinafter, the resin composition, resin sheet, circuit substrate, and semiconductor chip package of the present invention will be described in detail.

[Resin composition] The resin composition of the present invention contains: (A) a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkylene oxide structure, and a polyisopropylene oxide structure in the molecule; A polymer compound of one or more structures selected from a pentadiene structure, a polyisobutylene structure, and a polycarbonate structure, (B) epoxy resin, (C) thermally conductive filler, and (D) active ester hardener.

When the resin composition contains component (A), component (B), component (C), and component (D), a resin composition having excellent thermal conductivity, peeling strength of the metal layer, and warpage suppression can be obtained. Effective insulation. In addition, the aforementioned resin composition usually has low melt viscosity. The resin composition may further contain (E) hardener, (F) hardening accelerator, (G) inorganic filler (except those equivalent to component (C)) and (H) flame retardant when necessary. Each component contained in the resin composition will be described in detail below.

<(A) The molecule has a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkylene oxide structure, a polyisoprene structure, and a polyisobutylene structure. , and polymer compounds with one or more structures selected from the polycarbonate structure> The resin composition contains: (A) polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkylene oxide structure, and polyisoprene in the molecule A polymer compound with one or more structures selected from the structure, polyisobutylene structure, and polycarbonate structure. When the resin composition contains a polymer compound having these structures, warpage of the cured product can be suppressed. Moreover, "(meth)acrylate" means methacrylate and acrylate.

More specifically, component (A) is composed of a polybutadiene structure having polybutadiene, hydrogenated polybutadiene, etc., a polysiloxane structure having polysiloxane rubber, etc., and poly(meth)acrylate. Structure, polyalkylene structure (the polyalkylene structure with carbon atoms 2 to 15 is preferred, the polyalkylene structure with carbon atoms 3 to 10 is preferred, the polyalkylene structure with carbon atoms 5 to 6 is preferred is better), polyalkylene oxide structure (polyalkylene oxide structure with carbon atoms of 2 to 15 is preferred, polyalkylene oxide structure with carbon atoms of 3 to 10 is preferred, polyalkylene oxide structure with carbon atoms of 5 to 15 is preferred) The polyalkylene oxide structure of 6 is better), polyisoprene structure, polyisobutylene structure, and one or more structures selected from the polycarbonate structure, preferably those with polybutylene structure. One or more structures selected from ethylene structure, polysiloxane structure, poly(meth)acrylate structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure are preferred. Those having at least one structure selected from the group consisting of polybutadiene structure, polyisoprene structure, and polycarbonate structure are preferred.

From the viewpoint of expressing softness, component (A) is preferably one with a high molecular weight, and the number average molecular weight (Mn) is preferably 1,000 to 1,000,000, more preferably 5,000 to 9,00,000. The number average molecular weight (Mn) is the number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

From the viewpoint of expressing flexibility, component (A) is preferably one or more resins selected from a resin with a glass transition temperature (Tg) of 25°C or lower and a resin that is liquid at 25°C.

The glass transition temperature (Tg) is the glass transition temperature of the resin which is 25°C or lower, preferably 20°C or lower, more preferably 15°C or lower. The lower limit of the glass transition temperature is not particularly limited, but is usually -15°C or above. Furthermore, among resins that are liquid at 25°C, resins that are liquid at 20°C or lower are preferred, and resins that are liquid at 15°C or lower are more preferred.

From the viewpoint of improving the mechanical strength of the cured product, component (A) preferably has a functional group that can react with component (B). In addition, functional groups that can react with component (B) include, for example, functional groups that appear by heating.

In a preferred embodiment, the functional group that can react with component (B) is, for example, a group consisting of hydroxyl group, carboxyl group, acid anhydride group, phenolic hydroxyl group, epoxy group, isocyanate group and urethane group. One or more selected functional groups; among them, the functional group is, for example, a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group, preferably a hydroxyl group, an acid anhydride group , phenolic hydroxyl group and epoxy group are preferred, with phenolic hydroxyl group being particularly preferred.

A preferred embodiment of component (A) is butadiene resin. Among the butadiene resins, those that are liquid at 25°C or have a glass transition temperature of 25°C or less are preferred. The resins containing hydrogenated polybutadiene skeleton, butadiene resins containing hydroxyl groups, Butadiene resin containing phenolic hydroxyl group, butadiene resin containing carboxyl group, butadiene resin containing anhydride group, butadiene resin containing epoxy group, butadiene resin containing isocyanate group and aminomethyl group containing One or more resins selected from the group of butadiene resins with acid ester groups are preferred, and butadiene resins containing phenolic hydroxyl groups are more preferred. Resins containing hydrogenated polybutadiene skeleton, such as epoxy resin containing hydrogenated polybutadiene skeleton, etc. Butadiene resin containing phenolic hydroxyl groups is a resin having a polybutadiene structure and phenolic hydroxyl groups.

Among them, the term "butadiene resin" refers to a resin containing a polybutadiene structure. In these resins, the polybutadiene structure may be included in the main chain or in the side chain. The butadiene structure may be partially or completely hydrogenated. Among them, "resin containing hydrogenated polybutadiene skeleton" means a resin in which at least part of the polybutadiene skeleton is hydrogenated, and does not necessarily mean a resin in which the polybutadiene skeleton is completely hydrogenated.

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

When the butadiene resin has a functional group, the functional group equivalent is preferably 100 to 10,000, more preferably 200 to 5,000. In addition, the functional group equivalent means the number of grams of the resin containing 1 gram equivalent of the functional group. For example, the epoxy group equivalent can be measured in accordance with JIS K7236. The hydroxyl equivalent weight can be calculated by dividing the hydroxyl value measured according to JIS K1557-1 by the molecular weight of KOH.

Specific examples of butadiene resins include "Ricon 657" (epoxy-containing polybutadiene), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17", "Ricon 131 ... 184MA6" (polybutadiene containing anhydride groups), "JP-100" and "JP-200" (epoxy polybutadiene) made 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) made by DAICEL Co., Ltd., "EPFD A1005", "EPFD A1010", and "EPFD A1020" (epoxide of styrene, butadiene and styrene block copolymer), "FCA-061L" (epoxide of hydrogenated polybutadiene skeleton) and "R-45EPT" (epoxide of polybutadiene skeleton) manufactured by Nagase Chemical Co., Ltd.

Moreover, as another preferred embodiment of component (A), for example, a resin having an amide imine structure can be used. Resins having an amide structure, such as hydroxyl-terminated polybutadiene, diisocyanate compounds, and linear polyimides using tetrabasic acid anhydride as raw materials (Japanese Patent Application Publication No. 2006-37083, International Publication No. 2008/153208 Polyimide as described in the No.), etc. The polybutadiene structure content of the polyimide resin is preferably 60 mass% to 95 mass%, more preferably 75 mass% to 85 mass%. For details on the polyimide resin, please refer to the records in Japanese Patent Application Publication No. 2006-37083 and International Publication No. 2008/153208, and the contents are also incorporated into the records of this specification.

A preferred embodiment of component (A) is isoprene resin. Specific examples of the isoprene resin include "KL-610" and "KL-613" manufactured by KURARAY Co., Ltd. Here, "isoprene resin" means a resin containing a polyisoprene structure. In these resins, the polyisoprene structure may be included in the main chain or in the side chain.

Moreover, a preferred embodiment of component (A) is carbonate resin. The carbonate resin is preferably a carbonate resin with a glass transition temperature of 25°C or less. Carbonate resins containing hydroxyl groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, and carbonic acid containing acid anhydride groups are preferred. One or more resins selected from the group consisting of ester resin, epoxy group-containing carbonate resin, isocyanate group-containing carbonate resin, and urethane group-containing carbonate resin are preferred. Here, "carbonate resin" means a resin containing a polycarbonate structure. In these resins, the polycarbonate structure may be included in the main chain or in the side chain.

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

Specific examples of the carbonate resin include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., and "C-1090", "C-2090" and "C-3090" (polycarbonate diol) manufactured by KURARAY Co., Ltd. Carbonate diol) etc.

In addition, hydroxyl-terminated polycarbonate, diisocyanate compound, and linear polyimide using tetrabasic acid anhydride as a raw material can also be used. The polycarbonate structure content of the polyimide resin is preferably 60 mass% to 95 mass%, more preferably 75 mass% to 85 mass%. For details of the polyimide resin, please refer to the records in International Publication No. 2016/129541, and the contents are also incorporated into the records of this specification.

Another preferred embodiment of component (A) is acrylic resin. The acrylic resin is preferably an acrylic resin with a glass transition temperature (Tg) of 25°C or lower, and is preferably composed of an acrylic resin containing a hydroxyl group, an acrylic resin containing a phenolic hydroxyl group, an acrylic resin containing a carboxyl group, an acrylic resin containing an acid anhydride group, One or more resins selected from the group consisting of an epoxy group-containing acrylic resin, an isocyanate group-containing acrylic resin, and a urethane group-containing acrylic resin are preferred. Among them, "acrylic resin" means a resin containing a poly(meth)acrylate structure. In these resins, the poly(meth)acrylate structure may be included in the main chain or in the side chain. .

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. Here, the number average molecular weight (Mn) of the resin is the number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

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.

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

Moreover, another preferred embodiment of the component (A) is a siloxane resin, an alkyl resin, an alkoxy resin, or an isobutylene resin.

Specific examples of siloxane resins include "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shin-Etsu Polysiloxane Co., Ltd., amino-terminated polysiloxane, and tetrabasic acid anhydride is used as a raw material Linear polyimide (International Publication No. 2010/053185), etc. Here, "silicone resin" means a resin containing a polysiloxane structure. In these resins, the polysiloxane structure may be included in the main chain or in the side chain.

Specific examples of alkyl resins and alkoxy resins include, for example, "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Co., Ltd., and "YX-7180" manufactured by Mitsubishi Chemical Corporation (an alkyl alkylene group-containing resin with an ether bond). Structural resin), etc. "EXA-4850-150" made by DIC Corporation, "EXA-4816" "EXA-4822" made by ADEKA "EP-4000", "EP-4003", "EP-4010", and "EP-4011", new "BEO-60E" and "BPO-20E" manufactured by Japan Physical and Chemical Corporation, "YL7175" and "YL7410" manufactured by Mitsubishi Chemical Corporation, etc. Among them, "alkyl resin" means a resin containing a polyalkylene structure, and "alkoxy resin" means a resin containing a polyalkylene oxide structure. In these resins, the polyalkylene structure and the polyalkylene oxide structure may be included in the main chain or in the side chain.

Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by KANEKA Corporation. Here, "isobutylene resin" means a resin containing a polyisobutylene structure. In these resins, the polyisobutylene structure may be included in the main chain or in the side chain.

Another preferred embodiment of component (A) is, for example, acrylic rubber particles, polyamide particles, polysiloxane particles, and the like. Specific examples of acrylic rubber particles include chemically cross-linking resins such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber that exhibit rubber elasticity. They are microparticles of resin that are insoluble in organic solvents and do not melt. Specifically, for example, XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), SHUFFLE AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (above, manufactured by Kanz Chemical Co., Ltd.), PARALOID EXL2655, EXL2602 (above, Kureha) Chemical Industry Co., Ltd.), etc. Specific examples of the polyamide microparticles include aliphatic polyamides such as nylon, and those with a soft skeleton such as polyamideimide can be used. Specifically, for example, VESTOSINT 2070 (manufactured by DAICELHULS Co., Ltd.), SP500 (manufactured by Toray Co., Ltd.), and the like.

The content of component (A) in the resin composition, from the perspective of imparting flexibility, is when the non-volatile content (resin component) of the resin composition after removing component (C) and component (G) is set to 100% by mass. , preferably 65 mass% or less, more preferably 60 mass% or less, particularly preferably 55 mass% or less, most preferably 50 mass% or less. Moreover, the lower limit is preferably 10 mass% or more, more preferably 15 mass% or more, particularly preferably 20 mass% or more, and most preferably 25 mass% or more.

＜(B) Epoxy resin＞ The resin composition of the present invention contains epoxy resin as component (B). Component (B) is preferably an epoxy resin with an aromatic structure from the viewpoint of improving the effect of the present invention. Aromatic structures generally refer to chemical structures defined as aromatic, and also include polycyclic aromatic and aromatic heterocycles.

Epoxy resins, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, bicyclic Pentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-novolak-type epoxy resin, phenol-novolak-type epoxy resin, tert-butyl-catechol-type epoxy resin, naphthalene-type epoxy resin Oxygen resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin with aromatic structure, glycidyl ester type epoxy resin with aromatic structure, cresol-novolak type epoxy Resin, biphenyl epoxy resin, linear aliphatic epoxy resin with aromatic structure, epoxy resin with aromatic structure butadiene structure, alicyclic epoxy resin with aromatic structure, miscellaneous Cyclic epoxy resin, epoxy resin containing spiro ring with aromatic structure, cyclohexane dimethanol type epoxy resin with aromatic structure, naphthyl ether type epoxy resin, trimethylol with aromatic structure Base type epoxy resin, tetraphenylethane type epoxy resin, aminophenol type epoxy resin, etc. Epoxy resin can be used individually by 1 type, or in combination of 2 or more types. (B) Component is preferably at least one selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, aminophenol type epoxy resin and naphthalene type epoxy resin.

The epoxy resin is preferably an epoxy resin containing two or more epoxy groups per molecule. When the non-volatile content of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more of the non-volatile content of the epoxy resin is an epoxy resin having two or more epoxy groups per molecule. Among them, there are epoxy resins that have two or more epoxy groups in one molecule and are liquid at a temperature of 20°C (hereinafter also referred to as "liquid epoxy resins"), and those that have three epoxy groups in one molecule. The above epoxy groups and epoxy resins that are solid at a temperature of 20°C (hereinafter also referred to as "solid epoxy resin") are preferred. Epoxy resin, when liquid epoxy resin and solid epoxy resin are used together, a resin composition with excellent flexibility can be obtained. In addition, the fracture strength of the cured material of the resin composition can also be improved.

Liquid epoxy resin, such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, glycidyl ester-type epoxy resin with aromatic structure , glycidyl amine type epoxy resin with aromatic structure, phenol-novolak type epoxy resin, alicyclic epoxy resin with aromatic structure and ester skeleton, cyclohexane dimethanol type with aromatic structure Epoxy resin, aminophenol type epoxy resin and epoxy resin with aromatic structure butadiene structure are preferred, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type ring Oxygen resin, aminophenol type epoxy resin and naphthalene type epoxy resin are preferred, and bisphenol A type epoxy resin, bisphenol F type epoxy resin and aminophenol type epoxy resin are even more preferred. Specific examples of liquid epoxy resin include "HP4032", "HP4032D" and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, "828US" and "jER828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. Oxygen resin), "jER806", "jER807" (bisphenol F epoxy resin), "jER152" (phenol-novolak type epoxy resin), "630" (aminophenol type epoxy resin), "630LSD" ” (glycidyl amine type epoxy resin), “ZX1059” made by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), “EX” made by Nagase Chemical Co., Ltd. -721" (glycidyl ester type epoxy resin), "CELLOXIDE 2021P" made by DAICEL Co., Ltd. (alicyclic epoxy resin with ester skeleton), "ZX1658" and "ZX1658GS" made by Nippon Steel Chemical Co., Ltd. (liquid 1,4-glycidylcyclohexane), "YX7400" (high resilience epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

Solid epoxy resins, such as dixylenol-type epoxy resin, naphthalene-type 4-functional epoxy resin, cresol-novolak-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin Resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylene glycol Alkane type epoxy resin is preferred, with dixylenol type epoxy resin, naphthalene type 4-functional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthyl ether type epoxy resin being more preferred. The best ones are bixylenol type epoxy resin, naphthalene type 4-functional epoxy resin, naphthyl ether type epoxy resin, and biphenyl type epoxy resin. Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC Corporation (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" (dicyclopentadiene type epoxy resin) Epoxy resin), "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol-novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L" manufactured by Nippon Kayaku Co., Ltd. ", "NC3100" (biphenyl-type epoxy resin), "ESN475V" (naphthol-type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "ESN485" (naphthol-novolak type epoxy resin), Mitsubishi "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), "YL7760" (bisphenol AF-type epoxy resin), "YX8800" manufactured by Chemical Company (anthracene type epoxy resin), "PG-100" and "CG-500" made by Osaka Gas Chemical Co., Ltd., "YL7800" (anthracene type epoxy resin) made by Mitsubishi Chemical Co., Ltd., "jER1010" made by Mitsubishi Chemical Co., Ltd. (Solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), "157S70" (bisphenol-novolak type epoxy resin), "YX4000HK" manufactured by Mitsubishi Chemical Corporation (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100" and "CG-500" made by Osaka Gas Chemical Co., Ltd., "YL7800" (Fu) made by Mitsubishi Chemical Corporation type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

Among the components (B), when liquid epoxy resin and solid epoxy resin are used together, the quantitative ratio (solid epoxy resin: liquid epoxy resin) based on the mass ratio is 1 : The range of 0.1～1:15 is preferred. When the ratio of liquid epoxy resin to solid epoxy resin is within this range, i) when used in the form of resin sheets, it can have appropriate adhesiveness, ii) when used in the form of resin sheets, sufficient adhesion can be obtained. The flexibility can be improved to improve the handleability, and iii) a hardened product with sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the quantity ratio of liquid epoxy resin to solid epoxy resin (solid epoxy resin: liquid epoxy resin), based on the mass ratio, is 1 : The range of 0.3 to 1:10 is preferred, and the range of 1:0.6 to 1:8 is even more preferred.

The content of epoxy resin in the resin composition can produce an insulating layer with good mechanical strength and insulation reliability. When the non-volatile component in the resin composition is set to 100 mass %, it is preferably 1 mass. % or more, more preferably 2 mass % or more, particularly preferably 3 mass % or more. The upper limit of the epoxy resin content is not particularly limited as long as the effect of the present invention can be achieved. It is preferably 10 mass% or less, more preferably 8 mass% or less, and particularly preferably 6 mass% or less.

In addition, the content of the epoxy resin in the resin composition can produce an insulating layer with good mechanical strength and insulation reliability. When the non-volatile content is 100% by mass, it is 20% by mass or more, more preferably 25% by mass or more, and particularly preferably 30% by mass or more. The upper limit of the epoxy resin content is not particularly limited as long as the effect of the present invention can be achieved. It is preferably 70 mass% or less, more preferably 60 mass% or less, and particularly preferably 55 mass% or less.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, particularly preferably 80 to 2000, and most preferably 110 to 1000. Within this range, an insulating layer with sufficient cross-linking density and smaller surface roughness can be produced with the hardened material. In addition, the epoxy equivalent can be measured according to the provisions of JIS K7236, and is the mass of the resin containing 1 equivalent of epoxy groups.

The weight average molecular weight of the epoxy resin is preferably 100-5000, more preferably 250-3000, and particularly preferably 400-1500. The weight average molecular weight of the epoxy resin is the weight average molecular weight converted to polystyrene measured by gel permeation chromatography (GPC).

＜(C) Thermal conductive filler＞ The resin composition of the present invention contains (C) a thermally conductive filler. Here, in this specification, thermally conductive filler means an inorganic filler with a thermal conductivity of 20W/m·K or more.

The material of component (C) is not particularly limited as long as the thermal conductivity is within the above range. Materials containing component (C), such as aluminum oxide, aluminum nitride, boron nitride, silicon carbide, etc. Among these, alumina is particularly preferred. (C) Component can be used individually by 1 type, or in combination of 2 or more types. In addition, two or more types of the same materials may be used in combination.

The average particle diameter of the component (C) is preferably 5 μm or less, more preferably 4 μm or less, and particularly preferably 5 μm or less, from the viewpoint of obtaining an insulating layer having both excellent thermal conductivity and peel strength and improving filling properties. 3 μm or less; further, preferably 0.1 μm or more, more preferably 1.0 μm or more, particularly preferably 1.5 μm or more. (C) The average particle size of the component can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, for example, a laser diffraction and scattering particle size distribution measuring device is used to prepare the particle size distribution of the inorganic filler on a volume basis, and then the median number diameter is used as the average particle size. When measuring a sample, it is preferred to use ultrasonic waves to disperse component (C) in water. As a laser diffraction scattering particle size distribution measuring device, "LA-500" manufactured by Horiba Manufacturing Co., Ltd., "SALD2200" manufactured by Shimadzu Manufacturing Co., Ltd., etc. can be used. Specifically, for example, the measurement can be performed according to the method described in <Measurement of the average particle size of the thermally conductive filler> described later.

The specific surface area of the component (C) is preferably 0.5 m ² /g or more from the viewpoint of obtaining an insulating layer having both excellent thermal conductivity and peel strength and improving filling properties. (C) The specific surface area of the component is preferably 0.5m ² /g ~ 10m ² /g, and more preferably 0.5m ² /g ~ 5m ² /g. (C) The specific surface area of the component can be measured using the nitrogen BET method. Specifically, for example, an automatic specific surface area measuring device can be used for measurement. For example, an automatic specific surface area measuring device such as "Macsorb HM-1210" manufactured by MOUNTECH Co., Ltd. can be used. Specifically, for example, the measurement can be performed according to the method described in <Measurement of specific surface area of thermally conductive filler> described later.

In component (C), from the viewpoint of improving moisture resistance and dispersibility, one or more types of aminosilane coupling agent, epoxysilane coupling agent, sulfhydrosilane coupling agent, silane coupling agent, or Surface treatment agents such as alkoxysilane compounds, organosilazane compounds, and titanate coupling agents are used for treatment. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM803" (3-hydroxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. Trimethoxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. silane), "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM-4803" (long-chain epoxy silane coupling agent) manufactured by Shin-Etsu Chemical Industries, Ltd., etc. Among them, from the viewpoint of lowering the melt viscosity and improving lamination properties, component (C) is preferably surface-treated with an aminosilane coupling agent, and N-phenyl-3-aminopropyltrimethoxy is preferred. Starting from silane and N-phenyl-3-aminooctyltrimethoxysilane, it is better to use N-phenyl-3-aminoalkyltrimethoxysilane for surface treatment, and use N-phenyl-3- Surface treatment with aminooctyltrimethoxysilane is preferred.

The content of component (C) is preferably 85% by mass when the non-volatile content in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer having both excellent thermal conductivity and peel strength. % or more, more preferably 88 mass % or more, particularly preferably 89 mass % or more, or 90 mass % or more. The upper limit is preferably 95 mass% or less, more preferably 93 mass% or less, and particularly preferably 92 mass% or less.

＜(D) Active ester hardener＞ The resin composition of the present invention contains (D) active ester hardener. Active ester hardeners are not particularly limited, and are generally those with high reactivity such as phenolic esters, thiophenol esters, N-hydroxylamine esters, heterocyclic hydroxyl compound esters, etc. having two or more phenolic esters per molecule. Ester based compounds are preferred users. The active ester hardener is preferably prepared by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxyl compound and/or a thiol compound. Especially from the viewpoint of improving heat resistance, an active ester hardener prepared from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester hardener prepared from a carboxylic acid compound, a phenol compound and/or a naphthol compound is preferred. good. Carboxylic acid compounds, such as benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc. Phenolic 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, phloroglucinol, dicyclopentadienyl diphenol compound, phenol-phenolic aldehyde Varnish etc. Here, the "dicyclopentadiene-type diphenol compound" means a diphenol compound obtained by condensation of one molecule of dicyclopentadiene and two molecules of phenol.

Specifically, for example, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetate of phenol-novolac, and an active ester compound containing a phenol-novolak. Active ester compounds of benzoyl compounds are preferred, and among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are preferred. The "dicyclopentadiene-type diphenol structure" represents a bivalent structure formed by a phenylene-dicyclopentylene-phenylene group.

As the active ester compound, for example, those disclosed in Japanese Patent Application Laid-Open Nos. 2004-277460 and 2013-40270 can be used, or commercially available active ester compounds can be used. Commercially available active ester hardeners contain active ester compounds with a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H" -65TM", "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 acetyl compounds of phenol-novolac, such as "DC808" (manufactured by Mitsubishi Chemical Corporation), an active ester compound containing the benzyl compound of phenol-novolac, such as "YLH1026" (manufactured by Mitsubishi Chemical Corporation); an active ester hardener of the acetate compound of phenol-novolac, such as " DC808" (manufactured by Mitsubishi Chemical Corporation), active ester hardeners of benzyl compounds of phenol-novolaks such as "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi Chemical Corporation Co., Ltd.), "EXB9050L-62M" (a phosphorus atom-containing active ester compound) produced by DIC Co., Ltd., etc.

The content of component (D) is preferably 5 mass% or less, more preferably 3 mass% or less, and particularly preferably 2 mass% or less when the non-volatile content in the resin composition is 100 mass%. In addition, the lower limit is not particularly limited, but generally it is 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.

<(E) Hardening agent> The resin composition of the present invention may further contain (E) hardening agent in addition to component (D). In addition, the component (E) referred to here does not include (D) active ester hardener. (E) The hardener is not particularly limited as long as it has the function of hardening the resin of component (B), etc., for example, phenol-based hardener, naphthol-based hardener, benzox It is a hardener, cyanate ester hardener, carbodiimide hardener, etc. One type of hardening agent may be used alone, or two or more types may be used in combination. (D) Component is preferably one or more types selected from a phenol-based hardener, a naphthol-based hardener, and a cyanate ester-based hardener, and one or more types selected from a phenol-based hardener is preferred. .

Among the phenol-based hardeners and naphthol-based hardeners, from the viewpoint of heat resistance and water resistance, a phenol-based hardener having a novolac structure or a naphthol-based hardener having a novolac structure is preferred. In addition, from the viewpoint of adhesion to the wiring layer, a nitrogen-containing phenol-based hardener is preferred. A phenolic hardener for the skeleton is preferred. Among them, in terms of heat resistance, water resistance, and high adhesion to the wiring layer, the use of materials containing the three The skeleton phenol-novolac hardener is preferred.

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

Benzox Specific examples of the hardener include "HFB2006M" manufactured by Showa Polymer Co., Ltd., "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd., etc.

Cyanate ester hardeners, such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methyl-1,5-phenylene cyanate), 4,4'-phenylene cyanate Methyl bis(2,6-xylyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4- Cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-xylyl)methane, 1,3-bis(4- Bifunctional cyanate esters such as cyanatephenyl-1-(methylethylene)benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether Polyfunctional cyanate ester resins derived from resins, phenol-novolaks and cresol-novolacs, etc. These cyanate ester resins are partially Prepolymers obtained from Specific examples of cyanate ester hardeners include "PT30" and "PT60" manufactured by LONZA JAPAN (both are phenol-novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (both Part or all of phenol A dicyanate is treated with three Prepolymers that form trimers), etc.

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

When the resin composition contains component (E), the content of component (E) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it is preferably 5% by mass or less. , more preferably 3 mass% or less, particularly preferably 2 mass% or less. In addition, the lower limit is not particularly limited, but it is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more.

＜(F) Hardening accelerator＞ The resin composition of the present invention contains (F) a hardening accelerator. Examples of 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, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are more preferred. A hardening accelerator may be used individually by 1 type, or in combination of 2 or more types.

Phosphorus-based hardening accelerators include, for example, triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylboride, n-butylphosphonium tetraphenylboride, and tetrabutylphosphonium decanoate. , (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., and triphenylphosphine, tetrabutylphosphonium decanoate, etc. Salt is preferred.

Amine-based hardening accelerator, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-glycine (dimethylaminomethyl) Phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., and 4-dimethylaminopyridine, 1,8-diazabicyclo(5,4,0)-undecene, etc. One ene is better.

Imidazole-based hardening accelerators, such as 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-methyl Imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium salt trimellitate, 1-cyanoethyl-2-phenylimidazole salt trimellitic acid Ester, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-tri , 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 Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazole salt chloride, 2-methyl imidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds and epoxy resins, etc., and 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole Better.

Imidazole is a hardening accelerator, and commercially available products such as "P200-H50" manufactured by Mitsubishi Chemical Corporation can also be used.

Guanidine-based hardening accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dicyanodiamide. Methylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl- 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide , 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc., and Dicyanodiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

Metal-based hardening accelerators include, for example, organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylacetone (salt), cobalt (III) acetylacetone (salt), etc., copper (II) acetylacetone (salt) ), organic zinc complexes such as zinc (II) acetylacetone (salt), organic iron complexes such as iron (III) acetylacetone (salt), nickel (II ) organic nickel complexes such as acetylacetone (salt), organic manganese complexes such as manganese (II) acetylacetone (salt), etc. Organic metal salts include, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc.

When the resin composition contains component (F), the content of component (F) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is 100% by mass, it is 0.01% by mass. ~1% by mass is preferred.

＜(G) Inorganic filler (excluding components equivalent to (C))＞ The resin composition of the present invention may contain (G) inorganic filler. In addition, the (G) inorganic filler referred to here does not include the thermally conductive filler equivalent to (C). (G) The material of the component is not particularly limited, for example, silica, glass, cordierite, silicate, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, hydroaluminum Stone, 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 titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silicon dioxide is particularly suitable for use. In addition, the silica is preferably spherical silica. As for the inorganic filler, one type may be used alone or two or more types may be used in combination.

The average particle diameter of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, particularly preferably 2.2 μm or less, in order to produce an insulating layer with high circuit embedability and low surface roughness. Preferably, it is less than 2 μm. The lower limit of the average particle diameter is not particularly limited, but it is preferably 0.01 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more. The average particle size of the inorganic filler can be measured by the same method as component (C). Commercially available inorganic fillers having these average particle diameters include, for example, "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by ADMATECH, "UFP-30" manufactured by Denki Chemical Industry Co., Ltd. "SILFILE NSS-3N", "SILFILE NSS-4N", "SILFILE NSS-5N" made by Shan Co., Ltd., "SC2500SQ" made by ADMATECHS Co., Ltd., "SO-C6", "SO-C4", "SO-C2", " SO-C1" etc.

From the perspective of improving moisture resistance and dispersion, inorganic fillers are made of at least one aminosilane coupling agent, epoxysilane coupling agent, sulfhydrosilane coupling agent, silane coupling agent, and alkoxy coupling agent. It is preferable to use a surface treatment agent such as a silane compound, an organosilazane compound, or a titanate coupling agent. Specific commercially available surface treatment agents are as described above.

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

＜(H)Flame retardant＞ The resin composition may contain (H) a flame retardant. Flame retardants include, for example, organophosphorus flame retardants, phosphorus compounds containing organic nitrogen, nitrogen compounds, polysiloxane flame retardants, metal hydroxides, and the like. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more types.

As the flame retardant, commercially available products can also be used, such as "HCA-HQ" manufactured by Sanko Co., Ltd.

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

＜(I) Optional additives＞ The resin composition may contain other additives when necessary, such as organic copper compounds, organic zinc compounds, organic cobalt compounds and other organic metal compounds, as well as binders, tackifiers, defoaming agents, homogenizers, etc. Resin additives such as dyes, adhesion-imparting agents, and colorants.

＜Physical properties of resin composition＞ The cured product obtained by thermally hardening the resin composition of the present invention at 180°C for 30 minutes and then at 180°C for 60 minutes can exhibit excellent peel strength with a metal layer, especially a metal layer formed by plating. characteristic. That is, an insulating layer having excellent peel strength can be formed. Specifically, after the resin composition of the present invention is heat treated at 180°C for 30 minutes, a metal layer can be formed by plating on the roughened surface of the hardened material after the roughening treatment. After minute heat treatment, it can show the characteristics of excellent peel strength between the hardened material and the metal layer. The peel strength is preferably 0.4kgf/cm or more, more preferably 0.45kgf/cm or more, and particularly preferably 0.5kgf/cm or more. On the other hand, 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 evaluation of the peel strength can be performed according to the method described in <Measurement and Evaluation of the Tensile Peel Strength (Peel Strength) of the Metal Layer> described later. The metal layer is preferably a metal layer containing copper, and more preferably a metal layer formed by plating.

The cured product after the resin composition of the present invention is thermally cured at 180° C. for 90 minutes shows excellent thermal conductivity characteristics. That is, an insulating layer with excellent thermal conductivity. The thermal conductivity is preferably 1.5W/m·K or more, more preferably 1.8W/m·K or more, and particularly preferably 2.0W/m·K or more. The upper limit of thermal conductivity is 5.0W/m·K or less, 4.0W/m·K or less, or 3.5W/m·K or less. Thermal conductivity can be evaluated according to the method described in <Measurement of Thermal Conductivity of Hardened Material> described later.

The cured product after the resin composition of the present invention is thermally cured at 180°C for 90 minutes shows a low elastic modulus at 23°C. That is, an insulating layer having 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 0.1GPa or more. The elastic modulus can be measured according to the method described in <Measurement of elastic modulus> described later.

The cured product after the resin composition of the present invention is thermally cured at 100°C for 30 minutes and then at 180°C for 30 minutes shows the characteristics of low warpage. That is, an insulating layer with low warpage. The average amount of warpage of each of the four corners is preferably less than 1 cm. The amount of warpage can be measured according to the method described in <Evaluation of the amount of warpage> described later.

The resin composition of the present invention exhibits low melt viscosity. In this way, the lamination property of the resin composition layer of the resin sheet described later can be improved, and a cured product of the resin composition having high peel strength can be obtained. The melt viscosity is preferably 500 poise or more, more preferably 1,000 poise or more, and particularly preferably 1,500 poise or more; it is preferably 8,500 poise or less, more preferably 8,000 poise or less, and particularly preferably 7,500 poise or less, or 7,000 poise or less. Melt viscosity can be measured according to the method described in <Measurement of Melt Viscosity> described below.

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 suitably used as a resin composition for forming an insulating layer of a semiconductor chip package (a resin composition for an insulating layer of a semiconductor chip package) and a resin for forming an insulating layer of a circuit board (including a printed wiring board). The composition (resin composition for an insulating layer of a circuit board) is more suitably used for forming an interlayer insulating layer on a substrate on which a conductor layer is formed by plating (a circuit board in which a conductor layer is formed by plating, that is, A resin composition for the interlayer insulating layer of a circuit substrate formed by a Semi-Additive Process). Furthermore, it is also suitable for use in a resin composition for sealing semiconductor wafers (resin composition for semiconductor wafer sealing) and a resin composition for forming wiring on a semiconductor wafer (resin composition for semiconductor wafer wiring formation).

[Resin sheet] The resin sheet of the present invention includes a support body and a resin composition layer formed of the resin composition of the present invention provided on the support body.

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, 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 usually 1 μm or more, 5 μm or more, 10 μm or more, etc.

The support may be, for example, a film, metal foil, release paper, etc. made of plastic material, and preferably a film or metal foil made of plastic material.

When a film made of a plastic material is used as the support, the plastic material, for example, polyethylene terephthalate (hereinafter, also referred to as "PET"), polyethylene naphthyl ester (hereinafter, also referred to as "PEN") Polyesters such as polycarbonate (hereinafter also referred to as "PC"), acrylates such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether Sulfide (PES), polyetherketone, polyimide, etc. Among them, polyethylene terephthalate and polyvinyl naphthyl ester are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When metal foil is used as the support, the metal foil may be, for example, copper foil, aluminum foil, etc., and copper foil is preferred. The copper foil may be a foil made of a single metal of copper, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) .

The support can be subjected to matting treatment, corona treatment, etc. on the surface connected to the resin composition layer.

In addition, as the support, a support with a release layer and a release layer can be used on the surface where the resin composition layers are connected. The release agent used for the release layer as the support with the release layer is, for example, selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and polysiloxane resin. More than 1 type of release agent. As a support with a release layer, commercially available products can also be used. For example, PET films with a release layer mainly composed of alkyd resin release agents, such as "SK-1" and "AL" manufactured by Linde Co., Ltd. -5", "AL-7", "RUMINA T60" made by Toray, "PUREX" made by Teijin, "YUNIPIRE" made by UNITIKA, etc.

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

For a resin sheet, for example, a resin composition can be dissolved in an organic solvent to produce a resin coating, and then the resin coating can be applied on a support using a slit coater, a compression mold method, etc., and then dried to form a resin. Made in a layer-by-layer manner.

Organic solvents, such as acetone, methyl ethyl ketone (MEK), ketones such as cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carboxylic acid Acetates such as bitol acetate, cellosolve and carbitols such as butylcarbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetyl Amide solvents such as amine (DMAc) and N-methylpyrrolidone. One type of organic solvent may be used alone, or two or more types may be used in combination.

Drying can be performed using known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but are generally dried until the organic solvent content in the resin composition layer is 10% by mass or less, and preferably are dried to 5% by mass or less. It 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 organic solvent, the result is drying at 50°C to 150°C for 3 to 10 minutes, that is A resin composition layer can be formed.

On the surface of the resin sheet that is not connected to the support of the resin composition layer (that is, the surface opposite to the support), a protective film can be laminated together with the support. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating a protective film, impurities and the like can be prevented from adhering to or damaging the surface of the resin composition layer. Resin sheets can be rolled up into rolls and stored. When the resin sheet has a protective film, the protective film can be peeled off before use.

The resin sheet is suitable for use in the process of forming an insulating layer (insulating resin sheet for semiconductor chip packages) in the manufacture of semiconductor chip packages. For example, a resin sheet is suitably used to form an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board), and is more suitably used to form an interlayer insulating layer on a substrate to form a conductor layer through plating (a conductor layer is formed through plating). The interlayer insulation layer of the circuit substrate). Examples of packaging using these substrates include FC-CSP, MIS-BGA packaging, ETS-BGA packaging, etc.

In addition, the resin sheet is also suitable for use in sealing semiconductor wafers (resin sheet for semiconductor wafer sealing) or forming wiring on the semiconductor wafer (resin sheet for semiconductor wafer wiring formation), such as Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), Fan-in type PLP, etc. In addition, it is also suitable for use in MUF (Molding Under Filling) materials for connecting semiconductor wafers to substrates. In addition, the resin sheet is also suitable for use in a wide range of applications requiring high insulation reliability. For example, it is suitable for use in forming the insulating layer of circuit substrates such as printed wiring boards.

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

The sheet-like fiber substrate used for the prepreg is not particularly limited. Generally, glass fiber cloth, aromatic polyamide non-woven fabric, liquid crystal polymer non-woven fabric, etc. commonly used as prepreg substrates can be used. From the viewpoint of thinning, the thickness of the sheet-like fiber base material is preferably 900 μm or less, more preferably 800 μm or less, particularly preferably 700 μm or less, most preferably 600 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited, but is usually 1 μm or more, 1.5 μm or more, 2 μm or more, etc.

The prepreg can be produced according to known methods such as hot melt adhesive method and solvent method.

The thickness of the prepreg may be in the same range as the resin composition layer in the above-mentioned resin sheet.

[Circuit substrate] The circuit substrate of the present invention is an insulating layer formed of a cured product containing the resin composition of the present invention. The manufacturing method of the circuit substrate of the present invention includes: (1) The 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, (2) The step of laminating the resin sheet of the present invention on a base material with a wiring layer in such a manner that the wiring layer is embedded in the resin composition layer, and thermally curing it to form an insulating layer; (3) The step of forming connections between wiring layers. In addition, the manufacturing method of the circuit substrate may also include the step of (4) removing the base material.

In step (3), there is no particular limitation as long as the wiring layer can be connected between layers. The wiring layer is formed by forming a via hole in the insulating layer, and the insulation layer is Any step of grinding or grinding to expose the wiring layer is preferred.

＜Step (1)＞ Step (1) is a step of preparing a substrate and a substrate with a wiring layer having a wiring layer disposed on at least one side of the substrate. Usually, a base material with a wiring layer has a first metal layer and a second metal layer as part of the base material on both sides of the base material in sequence, and on the side of the base material with the second metal layer A wiring layer is formed on the opposite side. Specifically, a dry film (photosensitive resist film) is laminated on a base material, 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. After forming a wiring layer according to the electrolytic plating method, the patterned dry film is peeled off. In addition, the first metal layer and the second metal layer may not be provided.

The substrate includes, for example, a glass epoxy substrate, a metal substrate (stainless steel or cold-rolled steel plate (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or the like, It can also form a metal layer such as copper foil on the surface of the substrate. In addition, metal layers such as a peelable first metal layer and a second metal layer (for example, Mitsui Metals' ultra-thin copper foil with carrier copper foil, trade name "Micro Thin") may also be formed on the surface.

The dry film is not particularly limited as long as it is a photosensitive dry film formed of a photoresist composition. For example, dry films of novolac resin, acrylic resin, etc. can be used. Commercially available dry films can also be used.

The conditions for laminating the base material and the dry film are the same as the conditions for laminating the resin sheet into the wiring layer in step (2) described later, and the preferred range is also the same.

After the dry film is laminated on the substrate, a photomask can be used to make the dry film form the desired pattern, and it can be exposed and developed according to specific conditions.

The ratio of lines (line width)/space (width between lines) in the wiring layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), and more preferably 10/10 μm or less, especially Preferably it is below 5/5 μm, particularly preferably below 1/1 μm, and most preferably above 0.5/0.5 μm. The spacing does not need to be the same in all wiring layers. The minimum pitch of the wiring layer may be 40 μm or less, 36 μm or less, or 30 μm or less.

After the dry film pattern is formed, the wiring layer is formed, and the dry film is peeled off. Among them, the method of forming the wiring layer can be to use a dry film formed with a desired pattern as a plating mask and implement it according to the plating method.

The conductor material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer is selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. More than one kind of metal. The wiring layer may be a single metal layer or an alloy layer. The alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper-nickel alloy and copper-nickel alloy). Titanium alloy), etc. Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy is used from the viewpoint of the breadth of forming the wiring layer, cost, ease of pattern formation, etc. , copper-nickel alloy, copper-titanium alloy alloy layer 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 preferred , a single metal layer of copper is better.

The thickness of the wiring layer, depending on the desired design of the wiring board, is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, particularly preferably 10 to 20 μm, or 15 to 20 μm. In step (3), when the insulation layer is ground or ground to expose the wiring layer and form a connection between the layers, the thickness of the wiring connected between the layers and the thickness of the unconnected wiring is preferably different. . The thickness of the wiring layer can be adjusted by repeating the aforementioned pattern forming steps. Among the wiring layers, the thickness of the thickest wiring layer (conductive pillar) is preferably 2 μm or more and 100 μm or less depending on the desired design of the wiring board. In addition, the wiring connecting between layers may also have a convex shape.

After the wiring layer is formed, the dry film is peeled off. The dry film can be peeled off using, for example, an alkaline peeling liquid such as sodium hydroxide solution. If necessary, unnecessary wiring patterns can be removed through etching or the like to form desired wiring patterns. The spacing between the formed wiring layers is as described above.

＜Step (2)＞ Step (2) is a step of laminating the resin sheet of the present invention on a base material with a wiring layer in such a manner that the wiring layer is embedded in the resin composition layer, and then thermally hardening the resin sheet to form an insulating layer. In detail, the wiring layer of the substrate with the wiring layer obtained in the aforementioned step (1) is laminated in such a manner that the resin composition layer of the resin sheet is embedded, and then the resin composition layer of the resin sheet is thermally cured. and form an insulating layer.

The lamination method of the wiring layer and the resin sheet can be performed by, for example, heating and pressing the resin sheet onto the wiring layer from the support side after removing the protective film of the resin sheet. A member in which a resin sheet is heated and pressed against a wiring layer (hereinafter also referred to as a "heated pressing member") may be, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). In addition, instead of directly pressing the resin sheet with the heating and pressing member, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface irregularities of the wiring layer.

The lamination method of the wiring layer and the resin sheet can be implemented by using the vacuum lamination method after removing the protective film of the resin sheet. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and pressing pressure is preferably in the range of 0.098MPa to 1.77MPa, and more preferably 0.29MPa to 1.47 The range of MPa and the heating and pressing time are preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 13 hPa or less.

After lamination, the laminated resin sheets are smoothed under normal pressure (atmospheric pressure), for example, by pressing a heated pressing member from the support side. The pressure conditions for the smoothing treatment can be carried out under the same conditions as the heat pressing conditions for the above-mentioned lamination. In addition, lamination and smoothing processing can be performed continuously using the above-mentioned commercially available vacuum laminator.

The resin composition layer can be laminated on a base material with a wiring layer in which the wiring layer is embedded, and then the resin composition layer can be thermally cured to form an insulating layer. For example, the thermal hardening conditions of the resin composition layer vary depending on the type of resin composition, etc. Generally, the curing temperature is in the range of 120°C to 240°C, and the hardening time is in the range of 5 minutes to 120 minutes. Before thermally hardening the resin composition layer, the resin composition layer may also be preheated at a temperature lower than the curing temperature.

As a support for a resin sheet, a resin sheet may be laminated on a base material with a wiring layer and then peeled off after thermal curing. The support may be peeled off before laminating a resin sheet on a base material with a wiring layer. In addition, the support may be peeled off before the roughening step described below.

After the resin composition layer is thermally hardened to form an insulating layer, the surface of the insulating layer may also be polished. The grinding method is not particularly limited, and known methods may be used for grinding, such as using a plane grinding disc to grind the surface of the insulating layer.

＜Step (3)＞ Step (3) is a step of forming connections between wiring layers. The details include the steps of forming a via hole in the insulating layer, forming a conductor layer, and forming a connection between the wiring layers. Or the step of grinding or grinding the insulating layer to expose the wiring layer and form a connection between the wiring layers. The conductor layer is also called a wiring layer.

When using the steps of forming a through hole in the insulating layer, forming a conductor layer, and connecting the wiring layer between layers, the method of forming the through hole is not particularly limited, for example, laser irradiation, etching, mechanical drilling, etc. , and it is better to use laser irradiation. This laser irradiation can be performed using any laser processing machine whose light source is a carbonic acid gas laser, a YAG laser, an excimer laser, or the like. In detail, laser irradiation is performed from the supporting surface side of the resin sheet to penetrate the supporting body and the insulating layer, exposing the wiring layer to form a through hole.

The conditions for laser irradiation are not particularly limited. Laser irradiation can be carried out in accordance with the selected means and any appropriate steps according to ordinary methods.

The shape of the through hole, when viewed from the extending direction, is not particularly limited in the shape of the opening, and is generally circular (slightly circular).

After the through hole is formed, the stain in the through hole is removed, which is a so-called stain removal step. When the conductor layer is formed using the plating step described later, for example, a wet decontamination process can be performed on the through hole. When the conductor layer is formed using the sputtering step, for example, a dry decontamination process such as a plasma treatment step can be performed. steps. In addition, the stain removal step may also include a roughening step.

Before forming the conductor layer, the through holes and the insulating layer can be roughened. The roughening process can adopt commonly known procedures and conditions. Examples of dry roughening treatment include plasma treatment, and examples of wet roughening treatment include swelling treatment using a swelling liquid, roughening treatment using an oxidant, and neutralization using a neutralizing liquid in sequence. and processing methods.

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

After the via 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 conventionally known appropriate method such as plating, sputtering, and evaporation. Preferably, the conductor layer is formed by plating. In a preferred embodiment, for example, conventionally known techniques such as semi-additive process and full-additive process can be used to plate the surface of the insulating layer to form a desired wiring pattern. the conductor layer. Among them, the semi-additive method is the best. In the resin sheet, when the support is a metal foil, conventionally known techniques such as the subtractive process can be used to form a conductor layer having a desired wiring pattern. The conductor layer may have a single-layer structure, a single metal layer made of different types of metals or alloys, or a multi-layer structure in which two or more alloy layers are laminated.

The formation method using plating, specifically, uses electroless plating to form a plating seed layer on the surface of the insulating layer. Secondly, on the formed plating seed layer, a portion of the plating seed layer is exposed according to the desired wiring pattern to form a mask pattern. An electrolytic plating layer is formed on the exposed plating seed layer through electrolytic plating. At this time, while forming the electrolytic plating layer, a buried via (filled via) in which the via hole is buried using electrolytic plating may also be formed. After forming the electrolytic plating layer, the mask pattern is removed. Subsequently, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern. In addition, when forming the conductor layer, the dry film used when forming the mask pattern is the same as the dry film described above.

The conductor layer includes not only linear wiring, but also electrode pads (lands) carrying external terminals. Furthermore, the conductor layer may be composed only of electrode pads.

In addition, the conductor layer can be formed by forming the electrolytic plating layer and buried holes without using a mask pattern after forming the plating seed layer, and then patterning them by etching.

When using the step of grinding or grinding the insulating layer to expose the wiring layer and forming a connection between the layers, the grinding method or grinding method of the insulating layer can expose the wiring layer and make the grinding or grinding surface level. It is not particularly limited, and conventionally known polishing methods or grinding methods can be used, such as chemical mechanical polishing using a chemical mechanical polishing device, mechanical polishing of mirror surfaces, surface grinding of rotating abrasive grains, etc. The steps of forming a through hole on the insulating layer to form a conductor layer and connecting the wiring layer between layers are the same. It can be a stain removal step, a roughening step, or a conductor layer. Furthermore, it is not necessary to expose all the wiring layers, but only a part of the wiring layers may be exposed.

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

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.

[Semiconductor chip packaging] A first aspect of the semiconductor chip package of the present invention is a semiconductor chip package in which a semiconductor chip is mounted on the circuit substrate. The semiconductor chip package can be obtained by connecting the circuit substrate to the semiconductor chip.

As long as the terminal electrodes of the semiconductor chip can form conductive connections with the circuit wiring of the circuit board, the connection conditions are not particularly limited, and known conditions used in flip-chips on which semiconductor chips are actually mounted can be used. In addition, the semiconductor chip and the circuit board may be connected through an insulating adhesive.

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

In another preferred embodiment, the semiconductor chip is reflowed to the circuit substrate and connected. Reflow conditions are, for example, in the range of 120°C to 300°C.

After the semiconductor chip is connected to the circuit substrate, for example, the semiconductor chip can be filled with an underfill material (Underfill) to form a semiconductor chip package. The method of filling with the underfill material can be implemented using a known method. The resin composition or resin sheet of the present invention can also be used as an underfill material.

The second aspect of the semiconductor chip package of the present invention is, for example, the semiconductor chip package (Fan-out type WLP) as shown in FIG. 1 . The semiconductor chip package (Fan-out type WLP) 100 illustrated in FIG. 1 is a semiconductor chip package using a sealing layer 120 made of the resin composition or resin sheet of the present invention. The semiconductor chip package 100 is provided with a sealing layer 120 formed to cover the semiconductor wafer 110 and the periphery of the semiconductor wafer 110 , and a rewiring formation layer on the opposite side to the side of the sealing layer covering the semiconductor wafer 110 . (insulation layer) 130, conductor layer (rewiring layer) 140, solder resist layer 150, and bumps 160. The manufacturing methods of these semiconductor chip packages include: (A) The steps of laminating the pre-fixed film on the base material, (B) The step of pre-fixing the semiconductor wafer on the pre-fixing film, (C) The step of laminating the resin composition layer of the resin sheet of the present invention on the semiconductor wafer, or applying the resin composition of the present invention on the semiconductor wafer and thermally hardening it to form a sealing layer; (D) The step of peeling off the base material and the prefixed film from the semiconductor wafer, (E) The step of forming a rewiring formation layer (insulating layer) on the surface where the base material and the prefixed film are peeled off from the semiconductor wafer, (F) The step of forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer), and (G) The step of forming a solder resist layer on the conductor layer. Moreover, the manufacturing method of a semiconductor chip package also includes the step of (H) cutting a plurality of semiconductor chip packages into individual semiconductor chip packages and forming them into individual pieces.

＜Step (A)＞ Step (A) is a step of laminating the pre-fixed film on the base material. The lamination conditions of the base material and the prefixed film are the same as the lamination conditions of the wiring layer and the resin sheet in step (2) of the circuit board manufacturing method, and the preferred range is also the same.

The material used as the base material is not particularly limited. Substrates include, for example, silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, cold-rolled steel plates (SPCC), etc.; FR-4 substrates, etc., with glass fibers infiltrated with epoxy resin, etc. The substrate after thermal hardening treatment; Bismaleimide trisulfide such as BT resin Substrates made of resin, etc.

The material of the prefixing film is not particularly limited as long as it can be peeled off from the semiconductor wafer and prefix the semiconductor wafer in step (D) described below. Commercially available prefix films can be used. Commercially available products include, for example, LIWA-α manufactured by Nitto Denko Co., Ltd.

＜Step (B)＞ Step (B) is a step of pre-fixing the semiconductor wafer on the pre-fixing film. The semiconductor chip can be pre-fixed using known devices such as flip-chip connectors and die bonders. The arrangement and number of semiconductor wafers can be appropriately set according to the shape and size of the pre-fixing film, the number of target semiconductor packages to be produced, etc. For example, pre-fixing can be performed in a matrix-like arrangement with multiple rows and multiple columns. .

＜Step (C)＞ Step (C) is a step of laminating the resin composition layer of the resin sheet of the present invention on the semiconductor wafer, or coating the resin composition of the present invention on the semiconductor wafer and thermally hardening it to form a sealing layer. . In step (C), it is preferred that the resin composition layer of the resin sheet is laminated on the semiconductor wafer and thermally cured to form a sealing layer.

The method of laminating the semiconductor wafer and the resin sheet can be performed by, for example, heating and pressing the resin sheet onto the semiconductor wafer from the support side after removing the protective film from the resin sheet. A member that heats and presses a resin sheet onto a semiconductor wafer (hereinafter also referred to as a "heating and pressing member") may be, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). In addition, instead of directly pressing the resin sheet with the heating and pressing member, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet fully follows the unevenness of the surface of the semiconductor wafer.

In addition, the method of laminating the semiconductor wafer and the resin sheet can be implemented 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 the lamination conditions of the wiring layer and the resin sheet in step (2) of the circuit board manufacturing method, and the preferred range is also the same.

The support of the resin sheet may be peeled off after the resin sheet is laminated on the semiconductor wafer and thermally cured, or the support may be peeled off before the resin sheet is laminated on the semiconductor wafer.

The coating conditions of the resin composition are the same as the coating conditions when forming the resin composition layer in the resin sheet of the present invention, and the preferred ranges are also the same.

＜Step (D)＞ Step (D) is a step of peeling off the base material and the prefixed film from the semiconductor wafer. The peeling method can be appropriately changed according to the material of the pre-fixed film. For example, the pre-fixed film can be peeled off after heating, foaming (or expanding), and irradiating ultraviolet rays from the substrate side to reduce the risk of the pre-fixed film. Methods to peel off the adhesive force, etc.

In the method of heating, foaming (or expanding) the prefixed film and then peeling it off, the heating conditions are usually between 100°C and 250°C, and the heating is for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method of irradiating ultraviolet rays from the base material side to reduce the adhesive force of the prefixed film and peel it off, the amount of ultraviolet irradiation is usually 10mJ/cm ² to 1000mJ/cm ² .

＜Step (E)＞ Step (E) is a step of forming a rewiring formation layer (insulating layer) on the surface where the base material and the prefixed film are peeled off from the semiconductor wafer.

The material that can form the rewiring forming layer (insulating layer) is not particularly limited as long as it has insulating properties when forming the rewiring forming layer (insulating layer). From the viewpoint of ease of manufacturing the semiconductor chip package, Photosensitive resin and thermosetting resin are preferred. As the thermosetting resin, a resin composition having the same composition as the resin composition forming the resin sheet of the present invention can be used.

After the rewiring forming layer (insulating layer) is formed, a via hole may be formed in the rewiring forming layer (insulating layer) for the purpose of forming an interlayer connection between the semiconductor chip and a conductor layer described later.

When forming a through hole, if the material forming the rewiring forming layer (insulating layer) is a photosensitive resin, first, the surface of the rewiring forming layer (insulating layer) can be irradiated with active energy rays through the mask pattern, so that the irradiated part The rewiring layer is photohardened.

Active energy rays include, for example, ultraviolet rays, visible light, electron rays, X-rays, etc., and ultraviolet rays are particularly preferred. The amount and time of ultraviolet irradiation can be appropriately changed according to the photosensitive resin. The exposure method can be a contact exposure method in which the mask pattern is exposed in such a manner that the mask pattern is in close contact with the rewiring formation layer (insulation layer), and the mask pattern is not in close contact with the rewiring formation layer (insulation layer). Any non-contact exposure method that uses parallel light to expose can be used.

Next, the rewiring formation layer (insulating layer) is developed to remove the unexposed portion and form a through hole. For development, either wet development or dry development may be used. As the developer used for wet development, a well-known developer can be used.

Development methods include, for example, dipping, stirring, spraying, brushing, scraping, etc. From the viewpoint of resolution, the stirring method is preferred.

When the material forming the rewiring forming layer (insulating layer) is a thermosetting resin, the method of forming the through hole is not particularly limited, for example, laser irradiation, etching, mechanical drilling, etc., and laser irradiation is also used. Better. Laser irradiation can be performed using any appropriate laser processing machine whose light source is carbon dioxide laser, UV-YAG laser, excimer laser, etc.

The conditions for laser irradiation are not particularly limited. Laser irradiation can be carried out in accordance with the selected means and any appropriate steps according to ordinary methods.

The shape of the through hole, when viewed from the extending direction, is not particularly limited in the shape of the opening, and is generally circular (slightly circular). The top diameter of the through hole (the diameter of the opening on the surface of the rewiring formation 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 generally it is preferably 10 μm or more, more preferably 15 μm or more, and particularly preferably 20 μm or more.

＜Step (F)＞ Step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer). The method of forming the conductor layer on the rewiring formation layer (insulating layer) is the same as the method of forming the conductor layer after forming the through hole in the insulating layer in step (3) in the manufacturing method of the circuit board, and the preferred range is Same thing. In addition, steps (E) and (F) can also be repeated to form an alternate superposition (stack) of the conductor layer (rewiring layer) and the rewiring formation layer (insulating layer).

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

The material for forming the solder resist layer is not particularly limited as long as it has insulating properties when forming the solder resist layer. From the viewpoint of ease of manufacturing semiconductor chip packages, photosensitive resins and thermosetting resins are preferred. . As the thermosetting resin, a resin composition having the same composition as the resin composition forming the resin sheet of the present invention can be used.

Furthermore, in step (G), if necessary, bump processing may be performed to form bumps. The bump processing method can be performed using known methods such as solder balls and solder plating. In addition, in the bump processing, the through hole formation method can be carried out in the same method as step (E).

＜Step (H)＞ The manufacturing method of a semiconductor chip package may include a step (H) other than steps (A) to (G). Step (H) is a step of cutting the plurality of semiconductor wafer packages into individual semiconductor wafer packages to form individual wafers.

The method of cutting the semiconductor wafer package into individual semiconductor wafer packages is not particularly limited, and a known method can be used.

The third aspect of the semiconductor chip package of the present invention is, for example, the rewiring formation layer (insulating layer) 130 and the solder resist layer 150 in the semiconductor chip package (Fan-out type WLP) illustrated in FIG. 1 , a semiconductor chip package produced using the resin composition or resin sheet of the present invention.

[Semiconductor device] Semiconductor devices actually equipped with the semiconductor chip package of the present invention can be provided for use in electrical products (for example, computers, mobile phones, smartphones, tablet PC-type devices, wearable devices, digital cameras, medical equipment). , and televisions, etc.) and various semiconductor devices on board objects (such as motorcycles, cars, trains, ships, aircraft, etc.). [Example]

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited by these examples. In addition, in the following description, when "parts" and "%" of "amount" are expressed, unless otherwise stated, they mean "parts by mass" and "% by mass" respectively.

＜Preparation of samples for peel strength measurement＞ (1) Bottom layer treatment of inner circuit substrate Both sides of a glass cloth-based epoxy resin-coated copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, R5715ES manufactured by PANASONIC) with inner-layer circuits formed on both sides were immersed in CZ8100 manufactured by Mork Corporation. Roughening treatment of copper surface.

(2)Lamination of resin sheets The resin sheets prepared in the Examples and Comparative Examples were used in a batch vacuum pressure laminator (two-process stacking laminator "CVP700" manufactured by Nikko Metal Co., Ltd.) to connect the resin composition layer to the inner circuit substrate. method, laminated on both sides of the inner circuit substrate. The lamination method is to reduce the pressure for 30 seconds until the air pressure reaches 13hPa or less, and then press it for 30 seconds at 100°C and a pressure of 0.74MPa. Next, perform hot pressing for 60 seconds at 100°C and a pressure of 0.5MPa. The obtained laminate with a resin composition layer was heat-treated at 180° C. for 30 minutes to harden the resin composition layer, thereby producing a laminate with a hardened substance.

(3) Roughening treatment: The prepared laminate with hardened material was immersed in "Swelling Dip Securiganth P" (swelling fluid) containing diethylene glycol monobutyl ether manufactured by ATOTETCH Co., Ltd. of Japan at 60°C. 5 minutes, and then immersed in "Concentrate Compact P" (KMnO ₄ : 60g/L, NaOH: 40g/L aqueous solution, oxidizing agent (roughening liquid)) manufactured by Japan ATOTETCH Co., Ltd. at 80°C for 10 minutes, and finally At 40°C, the surface of the hardened material was roughened by immersing it in "Reduction Solution Security Gant P" (neutralizing solution) manufactured by Japan ATOTETCH Co., Ltd. for 5 minutes. The laminate obtained by the roughening process was used as evaluation substrate A.

(4) Metal layer formed by plating The evaluation substrate A was immersed in an electroless plating solution containing PdCl ₂ and then immersed in an electroless copper plating solution. Next, copper sulfate electrolytic plating is performed to form a metal layer with a thickness of 30 μm on the roughened surface of the hardened object. Next, annealing was performed at 180° C. for 60 minutes. The tempered laminate was used as evaluation substrate B.

<Measurement and evaluation of tensile peel strength (peel strength) of metal layers> Cut a 10mm wide and 100mm long portion of the metal layer of the evaluation substrate B, peel off one end, and clamp it with a clamp (AUTOCOM type testing machine "AC-50C-SL" manufactured by DSE Corporation), and place it at room temperature. , measure the load (kgf/cm) when pulling and peeling 20mm in the vertical direction at a speed of 50mm/min, and obtain the peeling strength.

＜Preparation of hardened material for elastic modulus evaluation＞ The untreated surface of the release PET film ("501010" manufactured by Linde Co., Ltd., thickness 38 μm, 240 mm square) was connected to a glass cloth base material and a copper-covered laminate on both sides of epoxy resin ("R5715ES" manufactured by Panasonic Electric Co., Ltd., thickness 0.7 mm , 255mm square), it is installed on the copper-covered laminate on both sides of the glass cloth base material epoxy resin. The four sides of the release PET film are fixed with polyimide adhesive tape (width 10mm).

Each resin sheet (167×107 mm square) prepared in the Examples and Comparative Examples was used to release PET using a batch vacuum pressure laminator (manufactured by Nikko Metal Co., Ltd., two-process stacking laminator, CVP700). The release surface of the film is connected to the resin composition layer, and the center is laminated. The lamination process is performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing for 30 seconds at 100° C. and a pressure of 0.74 MPa.

Next, the support was peeled off, and the resin composition layer was thermally cured under curing conditions of 180° C. and 90 minutes.

After thermal hardening, the polyimide adhesive tape is peeled off, and the resin composition layer is separated from the copper-covered laminate on both sides of the glass cloth base material epoxy resin. The release PET film is then peeled off from the resin composition layer to obtain a thin sheet-like cured product (cured product for evaluation).

＜Measurement of elastic modulus＞ The hardened material for evaluation was cut into a dumbbell-shaped No. 1 shape to prepare a test piece. The tensile strength of this test piece was measured using a tensile testing machine "RTC-1250A" manufactured by Orientec Corporation, and the elastic modulus at 23°C was obtained. The measurement method is based on JIS K7127. Repeat this operation three times, and the average value is shown in the table.

＜Evaluation of warpage＞ The resin sheets prepared in the Examples and Comparative Examples were laminated on the glass cloth base material BT resin on both sides using a batch vacuum pressure laminator (two-process stacking laminator "CVP700" manufactured by Nikko Metal Co., Ltd.). One side of the copper laminate (copper foil thickness 18 μm, substrate thickness 0.15 mm, "HL832NSF LCA" manufactured by Mitsubishi Gas Chemical Co., Ltd., size 15 cm After thermal hardening at 180°C for 30 minutes, place it on a flat surface to confirm the amount of warpage. The average amount of warpage at each of the four corners is marked as "○" if it is less than 1 cm, "△" if it is 1 to 2 cm, and "×" if it is more than 2 cm.

<Measurement of Thermal Conductivity of Hardened Materials> (1) Preparation of hardened material samples The resin coatings prepared in the Examples and Comparative Examples were coated with an alkyd resin release agent (manufactured by Linde Corporation) using a slit coater so that the thickness of the dried resin composition layer was 100 μm. "AL-5") is applied to a release-treated PET film ("LUMMIOR R80" manufactured by Toray Industries, thickness 38 μm, softening point 130°C), and then dried between 80°C and 100°C (average 90°C) After 7 minutes, a resin composition layer was obtained.

Using a batch-type vacuum pressure laminator (two-process stacking laminator "CVP700" manufactured by Nikko Metal Co., Ltd.), three resin composition layers were repeatedly laminated, and then laminated at 180°C for 90 minutes. Under hardening conditions, the resin composition layer is hardened to prepare a hardened material sample. The lamination method is to reduce the air pressure to less than 13hPa for 30 seconds, and then press it for 20 seconds at 100°C and a pressure of 0.4MPa.

(2) Measurement of thermal diffusivity α Using "ai-Phase Mobile 1u" manufactured by ai-Phase Co., Ltd., the thermal diffusivity α (m ² / s). The same sample was measured three times and the average value was calculated.

(3) Determination of specific heat capacity Cp The hardened material 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 Nanotechnology Co., Ltd.). Based on the measurement results, the temperature of the hardened material sample was calculated. Specific heat capacity Cp (J/kg·K) at 25℃.

(4) Measurement of density ρ The density (kg/m ³ ) of the hardened material sample was measured using an analytical balance XP105 manufactured by Mettler Toled Co., Ltd. (using a specific gravity measurement set).

(5) Thermal conductivity λ is calculated by using 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. , substitute into the following formula (I) to calculate the thermal conductivity λ (W/m・K). λ=α×Cp×ρ (I)

＜Measurement of melt viscosity＞ The melt viscosity of the resin composition layer in the resin sheets prepared in Examples and Comparative Examples was measured. Using UBM's model Rheosol-G3000, a parallel plate with a resin content of 1g and a diameter of 18mm, the measurement was carried out from the starting temperature of 60°C to 200°C, with a heating rate of 5°C/min, a measurement temperature interval of 2.5°C, and a vibration of 1Hz/deg. conditions to measure melt viscosity.

<Synthesis Example 1: Synthesis of Polymer Compound 1> In a reaction vessel, G-3000 (bifunctional hydroxyl-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g/eq., Solid content (100% by mass: Nippon Soda Co., Ltd.) 69g, 40g of IPUZOURU 150 (aromatic hydrocarbon mixed solvent: Idemitsu Petrochemical Co., Ltd.) and 0.005g of dibutyltin dilauryl ester were uniformly mixed and dissolved. After reaching a uniform state, the temperature was raised to 50°C, and while stirring, 8 g of isophorone diisocyanate (manufactured by Evonik Degussa Japan, IPDI, isocyanate group equivalent = 113 g/eq.) was added, and the reaction was carried out for about 3 hours. Next, the reaction product was cooled to room temperature, and 23 g of cresol-novolac resin (KA-1160, manufactured by DIC, hydroxyl equivalent = 117 g/eq.) was mixed with ethyl diethylene glycol acetate (manufactured by DAICEL) )60g was added to it, and the temperature was raised to 80°C while stirring, and the reaction was carried out for about 4 hours. Use FT-IR to confirm whether the NCO peak at 2250cm ^-1 has disappeared. When the NCO peak is confirmed to disappear, it is regarded as the end of the reaction. After cooling the reactant to room temperature, filter it using a filter cloth with a mesh of 100 μm to obtain a polymer compound 1 (non-volatile) with a polybutadiene structure and phenolic hydroxyl group. Ingredients 50% by mass).

<Synthesis Example 2: Synthesis of Polymer Compound 2> In a reaction vessel, polycarbonate diol (number average molecular weight: about 1,000, hydroxyl equivalent: 500, non-volatile content: 100%, "C-1015N" manufactured by KURARAY Co., Ltd. ") 80g, and 0.01g of dibutyltin dilauryl were uniformly dissolved in 37.6g of diethylene glycol monoethyl ether acetate ("ethyl diethylene glycol acetate" manufactured by DAICEL). Next, the temperature of the mixture was raised to 50°C, and 27.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent: 87.08) was added while stirring, and the reaction was carried out for about 3 hours. Next, the reactant was cooled to room temperature, and 14.3 g of benzophenone tetracarboxylic dianhydride (anhydride equivalent: 161.1), 0.12 g of triethylene diamine, and diethylene glycol monoethyl ether acetate (manufactured by DAICEL) were added. "Ethyl diethylene glycol acetate") 84.0g was added therein, and the temperature was raised to 130°C while stirring, and the reaction was carried out for about 4 hours. Use FT-IR to confirm whether the NCO peak at 2250cm ^-1 has disappeared. When the NCO peak is confirmed to disappear, it is regarded as the end of the reaction. After cooling the reactant to room temperature, filter it using a filter cloth with a mesh of 100 μm to obtain a polymer compound 2 with a carbonate structure (non-volatile content 50% by mass).

<Measurement of average particle size of thermally conductive filler> In a 20ml vial, add 0.01g of thermally conductive filler, 0.2g of nonionic dispersant ("T208.5" manufactured by Nippon Oils and Fats Co., Ltd.), and 10g of pure water, and perform ultrasonic dispersion for 10 minutes using an ultrasonic cleaner. Prepare samples. Next, the sample was put into a laser diffraction particle size distribution measuring device ("SALD2200" manufactured by Shimadzu Corporation) and irradiated with ultrasonic waves for 10 minutes while circulating. Subsequently, the ultrasonic wave was stopped and the particle size distribution was measured while the sample was maintained in a circulating state to obtain the average particle size of the thermally conductive filler. In addition, the refractive index during measurement was set to 1.45-0.001i.

<Measurement of specific surface area of thermally conductive filler> The specific surface area was determined by the azido BET method using an automatic specific surface area measuring device ("Macsorb HM-1210" manufactured by MOUNTECH).

<Thermal conductive filler used> Alumina 1: A mixture of alumina with different average particle diameters and specific surface areas, with an average particle diameter of 3 μm and a specific surface area of 1.5 m ² /g, manufactured by Shin-Etsu Chemical Industry Co., Ltd. "KBM573" ( N-phenyl-3-aminopropyltrimethoxysilane) surface treatment alumina 2: a mixture of alumina with different average particle diameters and specific surface areas, with an average particle diameter of 3 μm and a specific surface area of 1.5 m ² /g , surface treated with "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Alumina 3: A mixture of alumina with different average particle diameters and specific surface areas, average Alumina 4 with a 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 Industry Co., Ltd.: Average particle size and specific surface area A mixture of different aluminum oxides with an average particle diameter of 3 μm and a specific surface area of 1.5 m ² /g, which has been surface-treated with "KBM903" (3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd.

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

Resin paint 1 is applied using a slit coater so that the thickness of the dried resin composition layer is 50 μm, and is coated on a surface treated with an alkyd resin release agent ("AL-5" manufactured by Linde Corporation). Then, on the PET film ("LUMMIOR R80" manufactured by Toray, thickness 38 μm, softening point 130°C, also called "release PET"), dry it for 5 minutes between 80°C and 100°C (average 90°C) , to obtain resin sheet 1.

<Example 2> Mix 6 parts of aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g/eq), liquid epoxy resin ("ZX1059" manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation, bisphenol A type ring 1:1 mixture (mass ratio) of oxy resin and bisphenol F epoxy resin, epoxy equivalent: 169g/eq) 5 parts, dixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy Equivalent: 185g/eq) 2 parts of biphenyl-type epoxy resin (Nihon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258g/eq), dissolve in 10 parts of methyl ethyl ketone, and then mix alumina 1 270 parts, 24 parts of polymer compound 1 (solid content 50 mass%, number average molecular weight 5500), active ester hardener (DIC company "HPC-8000-65T", active ester equivalent 223g/eq, solid content 65% Toluene solution) 6 parts, solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., hydroxyl equivalent 215g/eq, used as a methyl ethyl ketone solution with a solid content of 50%), 6 parts, hardened 1 part of accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with 10% solid content by mass) and 15 parts of methyl ethyl ketone were evenly dispersed using a high-speed rotary mixer to prepare a resin. Paint 2. Moreover, in Example 1, the resin sheet 2 was produced in the same manner as in Example 1, except that the resin paint 1 was changed to the resin paint 2.

<Example 3> Mix 6 parts of aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g/eq), liquid epoxy resin ("ZX1059" manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation, bisphenol A type ring 1:1 mixture (mass ratio) of oxy resin and bisphenol F epoxy resin, epoxy equivalent: 169g/eq) 5 parts, dixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy Equivalent: 185g/eq) 2 parts of biphenyl-type epoxy resin (Nihon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258g/eq), dissolve in 10 parts of methyl ethyl ketone, and then mix alumina 1 240 parts, 24 parts of polymer compound 1 (solid content 50 mass%, number average molecular weight 5500), active ester hardener (DIC company "HPC-8000-65T", active ester equivalent 223g/eq, solid content 65% Toluene solution) 3 parts, solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., hydroxyl equivalent 215g/eq, used as methyl ethyl ketone solution with 50% solid content), 2 parts, hardened 1 part of accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with 10% solid content by mass) and 15 parts of methyl ethyl ketone were evenly dispersed using a high-speed rotary mixer to prepare a resin. Paint 3. In addition, in Example 1, except that the resin paint 1 was changed to the resin paint 3, the resin sheet 3 was produced in the same manner as in Example 1.

<Example 4> Mix 6 parts of aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g/eq), liquid epoxy resin ("ZX1059" manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation, bisphenol A type ring 1:1 mixture (mass ratio) of oxy resin and bisphenol F epoxy resin, epoxy equivalent: 169g/eq) 5 parts, dixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy Equivalent: 185g/eq) 2 parts of biphenyl-type epoxy resin (Nihon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258g/eq), dissolve in 10 parts of methyl ethyl ketone, and then mix alumina 2 270 parts, 24 parts of polymer compound 1 (solid content 50 mass%, number average molecular weight 5500), active ester hardener (DIC company "HPC-8000-65T", active ester equivalent 223g/eq, solid content 65% Toluene solution) 3 parts, solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., hydroxyl equivalent 215g/eq, used as methyl ethyl ketone solution with 50% solid content), 2 parts, hardened 1 part of accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with 10% solid content by mass) and 15 parts of methyl ethyl ketone were evenly dispersed using a high-speed rotary mixer to prepare a resin. Paint 4. Moreover, in Example 1, the resin sheet 4 was produced in the same manner as in Example 1, except that the resin paint 1 was changed to the resin paint 4.

<Example 5> Mix 6 parts of aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g/eq), liquid epoxy resin ("ZX1059" manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation, bisphenol A type ring 1:1 mixture (mass ratio) of oxy resin and bisphenol F epoxy resin, epoxy equivalent: 169g/eq) 5 parts, dixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy Equivalent: 185g/eq) 2 parts of biphenyl-type epoxy resin (Nihon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258g/eq), dissolve in 10 parts of methyl ethyl ketone, and then mix alumina 1 270 parts, 24 parts of polymer compound 2 (solid content 50 mass%, number average molecular weight 6000), active ester hardener (DIC company "HPC-8000-65T", active ester equivalent 223g/eq, solid content 65% Toluene solution) 3 parts, solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., hydroxyl equivalent 215g/eq, used as methyl ethyl ketone solution with 50% solid content), 2 parts, hardened 1 part of accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with 10% solid content by mass) and 15 parts of methyl ethyl ketone were evenly dispersed using a high-speed rotary mixer to prepare a resin. Paint 5. Moreover, in Example 1, the resin sheet 5 was produced in the same manner as in Example 1, except that the resin paint 1 was changed to the resin paint 5.

＜Comparative example 1＞ Mix 6 parts of aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g/eq), liquid epoxy resin ("ZX1059" manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation, bisphenol A type ring 1:1 mixture (mass ratio) of oxy resin and bisphenol F epoxy resin, epoxy equivalent: 169g/eq) 5 parts, dixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy Equivalent: 185g/eq) 2 parts of biphenyl-type epoxy resin (Nihon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258g/eq), dissolve in 10 parts of methyl ethyl ketone, and then mix alumina 1 270 parts, 24 parts of polymer compound 1 (solid content 50 mass %, number average molecular weight 5500), solid naphthol-based hardener ("SN485" manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd., hydroxyl equivalent 215 g/eq, in solid form 6 parts of methyl ethyl ketone solution with 50% content), 1 part of hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with 10 mass% solid content), 1 part of methyl 15 parts of ethanol are evenly dispersed using a high-speed rotary mixer to prepare resin coating 6. Moreover, in Example 1, the resin sheet 6 was produced in the same manner as in Example 1, except that the resin paint 1 was changed to the resin paint 6.

＜Comparative example 2＞ Mix 6 parts of aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g/eq), liquid epoxy resin ("ZX1059" manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation, bisphenol A type ring 1:1 mixture (mass ratio) of oxy resin and bisphenol F epoxy resin, epoxy equivalent: 169g/eq) 5 parts, dixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy Equivalent: 185g/eq) 2 parts of biphenyl-type epoxy resin (Nihon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258g/eq), dissolve in 10 parts of methyl ethyl ketone, and then mix alumina 1 270 parts, 26 parts of polymer compound 1 (solid content 50 mass %, number average molecular weight 5500), solid naphthol-based hardener ("SN485" manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd., hydroxyl equivalent 215g/eq, in solid form 2 parts of methyl ethyl ketone solution with 50% content), 1 part of hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with 10 mass% solid content), 1 part of methyl 15 parts of ethanol were evenly dispersed using a high-speed rotary mixer to prepare resin coating 7. Furthermore, in Example 1, except that the resin paint 1 was changed to the resin paint 7, the resin sheet 7 was produced in the same manner as in Example 1.

＜Comparative Example 3＞ Mix 6 parts of aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g/eq), liquid epoxy resin ("ZX1059" manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation, bisphenol A type ring 1:1 mixture (mass ratio) of oxy resin and bisphenol F epoxy resin, epoxy equivalent: 169g/eq) 5 parts, dixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy Equivalent: 185g/eq) 2 parts of biphenyl-type epoxy resin (Nihon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258g/eq), dissolve in 10 parts of methyl ethyl ketone, and then mix alumina 3 270 parts, 24 parts of polymer compound 1 (solid content 50 mass %, number average molecular weight 5500), solid naphthol-based hardener ("SN485" manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd., hydroxyl equivalent 215 g/eq, in solid form 6 parts of methyl ethyl ketone solution with 50% content), 1 part of hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with 10 mass% solid content), 1 part of methyl 15 parts of ethanol were evenly dispersed using a high-speed rotary mixer to prepare resin coating 8. Moreover, in Example 1, the resin sheet 8 was produced in the same manner as in Example 1, except that the resin paint 1 was changed to the resin paint 8.

＜Comparative Example 4＞ Mix 6 parts of aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g/eq), liquid epoxy resin ("ZX1059" manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation, bisphenol A type ring 1:1 mixture (mass ratio) of oxy resin and bisphenol F epoxy resin, epoxy equivalent: 169g/eq) 5 parts, dixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000H", epoxy Equivalent: 185g/eq) 2 parts of biphenyl-type epoxy resin (Nihon Kayaku Co., Ltd. "NC3100", epoxy equivalent: 258g/eq), dissolve in 10 parts of methyl ethyl ketone, and then mix alumina 4 270 parts, 24 parts of polymer compound 1 (solid content 50 mass%, number average molecular weight 5500), solid naphthol-based hardener ("SN485" manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd., hydroxyl equivalent 215g/eq, in solid form 6 parts of methyl ethyl ketone solution with 50% content), 1 part of hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with 10 mass% solid content), 1 part of methyl 15 parts of ethanol were evenly dispersed using a high-speed rotary mixer to prepare resin coating 9. Furthermore, in Example 1, except that the resin paint 1 was changed to the resin paint 9, the resin sheet 9 was produced in the same manner as in Example 1.

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

As shown in Examples 1 to 5, the insulating layer formed of the resin composition containing components (A) to (D) exhibits excellent peel strength. On the other hand, it was confirmed that the peel strength of Comparative Examples 1 to 4, which did not contain component (D), was inferior to that of Examples 1 to 5. In addition, it was found that Comparative Examples 3 to 4 in which the component (C) was not treated with N-phenyl-3-aminoalkyltrimethoxysilane had a melt viscosity that was too high, so the lamination properties were deteriorated and the peel strength was also inferior. In addition, it was found that in Examples 1 to 5, even when the component (E) and the component (F) are not contained, the examples with degree differences are the same as those in the above-mentioned Examples, and the same results are attributed.

100:Semiconductor chip packaging 110:Semiconductor wafer 120:Sealing layer 130: Rewiring formation layer (insulating layer) 140: Conductor layer (rewiring layer) 150: Solder resist layer 160:Bump

[Fig. 1] Fig. 1 is a schematic cross-sectional view of an example of the semiconductor chip package (Fan-out type WLP) of the present invention.

Claims (19)

A resin composition characterized by containing: (A) polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkyleneoxy structure, poly Polymer compound of one or more structures selected from isoprene structure, polyisobutylene structure, and polycarbonate structure, (B) epoxy resin, (C) thermally conductive filler, and (D) active ester hardener , wherein (A) the component coefficient average molecular weight (Mn) is 1,000~1,000,000, or one or more resins selected from resins with a glass transition temperature (Tg) of 25°C or less, and resins that are liquid at 25°C , when the resin component in the resin composition is set to 100% by mass, the content of component (A) is 20% by mass or more, and the elastic modulus of the cured product of the resin composition after thermal curing at 180°C for 90 minutes is 11GPa or more. Below 20 GPa, the melt viscosity of the resin composition is above 1000 poise and below 7000 poise. The resin composition of claim 1, wherein the peel strength of the hardened product formed by thermal hardening of 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: 0.4kgf/cm or more. For example, the resin composition of claim 1, wherein the content of component (C) is 100% by mass of non-volatile components in the resin composition When, it is more than 85 mass%. The resin composition of claim 1, wherein component (C) contains alumina. The resin composition of claim 1, wherein component (C) is surface-treated with an aminosilane coupling agent. The resin composition of claim 1, wherein component (C) is surface-treated with N-phenyl-3-aminoalkyltrimethoxysilane. The resin composition of Claim 1, wherein the thermal conductivity of the cured product formed by thermally curing the resin composition at 180°C for 90 minutes is 1.5W/m‧K or more and 5.0W/m‧K or less. The resin composition of claim 1, wherein the component (A) is at least one selected from a resin having a glass transition temperature of 25°C or less and a resin that is liquid at 25°C. The resin composition of claim 1, wherein component (A) has a functional group that can react with component (B). The resin composition of claim 1, wherein component (A) has one or more functional groups selected from the group consisting of hydroxyl group, acid anhydride group, phenolic hydroxyl group, epoxy group, isocyanate group and urethane group. The resin composition of claim 1, wherein component (A) has an amide imine structure. The resin composition of claim 1, wherein component (A) has a phenolic hydroxyl group. The resin composition of claim 1, wherein component (A) has a polybutadiene structure and has a phenolic hydroxyl group. The resin composition of claim 1 is a resin composition for the insulating layer of semiconductor chip packaging. The resin composition of claim 1 is a resin composition for the insulating layer of a circuit substrate formed by a semi-additive process. A resin sheet, characterized by having: a support body; and a resin composition layer including the resin composition of any one of claims 1 to 15 provided on the support body. A circuit substrate, characterized by comprising: an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 15. A semiconductor chip package, characterized by comprising: the circuit substrate of claim 17, and a semiconductor chip mounted on the circuit substrate. A semiconductor chip package, characterized by comprising: the resin composition of any one of claims 1 to 15, or a semiconductor chip sealed by the resin sheet of claim 16.

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