TWI779019B - resin composition - Google Patents

Abstract

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

Description

resin composition

The present invention relates to resin compositions. Also, it relates to resin sheets using resin compositions, circuit boards, and semiconductor chip packages.

In recent years, along with miniaturization and higher functionality of electronic equipment, the mounting density of semiconductor elements in printed wiring boards tends to increase. Along with the higher functionality of mounted semiconductor devices, a technology capable of efficiently dissipating heat generated by semiconductor devices has been sought. When the resin composition containing the thermally conductive filler is hardened to form an insulating layer, based on increasing the content of the thermally conductive filler in the resin composition, the thermal conductivity of the resulting insulating layer can be improved, but the content of the thermally conductive filler is increased to When sufficient thermal conductivity is generated, the resulting insulating layer tends to deteriorate in its adhesion strength to the metal layer on which wiring is to be formed.

For example, in Patent Document 1, it is disclosed that when a printed wiring board using a resin composition containing aluminum nitride or silicon nitride is cured to form an insulating layer, in addition to generating thermal diffusivity, it has low surface roughness. The adhesion strength (peel strength) of the conductor layer can make the content of heat diffusion good. [Prior Art Document] [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-performance of electronic equipment, in the process of thinning and shell-free substrates, in addition to thermal diffusivity and adhesion strength (peel strength), a material is also sought. It can suppress the warping phenomenon that occurs when the insulating layer is formed. These properties have a trade-off relationship, so it is very difficult to design a balanced resin.

The present invention is proposed in view of solving the above-mentioned problems, and provides a kind of material that can be obtained with excellent thermal conductivity, excellent peel strength to the metal layer, and a balance between the amount of warpage that occurs when the insulating layer is formed. Resin composition of cured product; resin sheet, circuit board, and semiconductor chip package using the resin composition. [How to solve the problem]

The present inventors found that it contains: (A) polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkylene oxide structure, polyisoamyl Composition of 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 material having excellent thermal conductivity, excellent peel strength to a metal layer (in particular, a metal layer formed by plating), and an excellent effect in suppressing warpage that occurs when an insulating layer is formed. insulating layer, thus completing the invention.

That is, the present invention includes the following matters. [1] A resin composition characterized in that it contains: (A) It has a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, and a polyalkylene structure in the molecule. Oxygen structure, polyisoprene structure, polyisobutylene structure, and polymer compound of one or more structures selected from polycarbonate structure, (B) epoxy resin, (C) thermally conductive filler, and (D) Active ester hardener. [2] The resin composition as described in [1], wherein the cured product formed by heat curing the resin composition at 180°C for 30 minutes and then at 180°C for 60 minutes, and the metal layer formed by plating The peel strength is above 0.4kgf/cm. [3] The resin composition as described in [1] or [2], wherein the content of component (C) is 85% by mass or more when the non-volatile 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 as described in any one of [1] to [4], wherein the component (C) is surface-treated with an aminosilane-based coupling agent. [6] The resin composition described in any one of [1] to [5], wherein the 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 1.5 W/m· Above K, below 5.0W/m・K. [8] The resin composition according to any one of [1] to [7], wherein the component (A) is selected from resins having a glass transition temperature of 25°C or lower and resins that are liquid at 25°C. One or more of them. [9] The resin composition according to any one of [1] to [8], wherein the component (A) has a functional group capable of reacting with the component (B). [10] The resin composition according to any one of [1] to [9], wherein the component (A) has a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a carbamic acid group. One or more functional groups selected from the ester group. [11] The resin composition according to any one of [1] to [10], wherein the component (A) has an imide structure. [12] The resin composition according to any one of [1] to [11], wherein the component (A) has a phenolic hydroxyl group. [13] The resin composition according to any one of [1] to [12], wherein the component (A) has a polybutadiene structure and has a phenolic hydroxyl group. [14] The resin composition as described in any one of [1] to [13], which is a resin composition for an insulating layer of a semiconductor chip package. [15] The resin composition as described in any one of [1] to [14], which is a resin composition for an insulating layer of a circuit board formed by using a semi-additive process (Semi-Additive Process). [16] A resin sheet characterized by comprising: a support, and a resin composition layer comprising the resin composition described in any one of [1] to [15] provided on the support. [17] A circuit board characterized by comprising: an insulating layer formed of a cured product of the resin composition described in 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 by the resin composition described in any one of [1] to [15], or the resin sheet described in [16]. [Effect of Invention]

According to the content of the present invention, it is possible to provide a metal layer with excellent thermal conductivity, excellent adhesion strength to a metal layer, especially a metal layer formed by plating, and to suppress the amount of warpage that occurs when an insulating layer is formed. A resin composition capable of obtaining a balanced cured product; a resin sheet, a circuit substrate, and a semiconductor chip package using the resin composition.

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

[Resin Composition] The resin composition of the present invention contains: (A) polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkylene structure in the molecule Oxygen structure, polyisoprene structure, polyisobutylene structure, and polymer compound with at least one structure selected from polycarbonate structure, (B) epoxy resin, (C) thermally conductive filler, and (D) Active ester hardener.

When a resin composition containing (A) component, (B) component, (C) component, and (D) component is used, a resin composition with excellent thermal conductivity, peel strength to the metal layer, and excellent warpage suppression can be obtained. effect of insulating layer. Also, the aforementioned resin composition generally has a low melt viscosity. The resin composition may further contain (E) hardener, (F) hardening accelerator, (G) inorganic filler (excluding those corresponding to (C) component) and (H) flame retardant if necessary. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Molecule has polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkylene oxide structure, polyisoprene structure, polyisobutylene structure , and polymer compounds with more than one structure selected from the polycarbonate structure> The resin composition contains: (A) a polybutadiene structure, polysiloxane structure, poly(meth)acrylic acid in the molecule A polymer compound having at least one structure selected from ester structure, polyalkylene structure, polyalkylene oxide structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure. When the polymer compound having these structures is contained in the resin composition, warpage of the cured product can be suppressed. In addition, "(meth)acrylate" means methacrylate and acrylate.

More specifically, component (A) consists of a polybutadiene structure such as polybutadiene and hydrogenated polybutadiene, a polysiloxane structure such as polysiloxane rubber, and a poly(meth)acrylate Structure, polyalkylene structure (preferably polyalkylene structure with 2 to 15 carbon atoms, preferably polyalkylene structure with 3 to 10 carbon atoms, and polyalkylene structure with 5 to 6 carbon atoms is more preferable), polyalkylene oxide structure (preferably the polyalkylene oxide structure with 2 to 15 carbon atoms, preferably the polyalkylene oxide structure with 3 to 10 carbon atoms, and the polyalkylene oxide structure with 5 to 10 carbon atoms 6 polyalkylene oxide structure is more preferred), polyisoprene structure, polyisobutylene structure, and one or more structures selected from polycarbonate structures are preferred, with polybutylene One or more structures selected from polyene structure, polysiloxane structure, poly(meth)acrylate structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure are preferred. It is preferable to have one or more structures selected from polybutadiene structure, polyisoprene structure, and polycarbonate structure.

The component (A) preferably has a high molecular weight from the viewpoint of expressing flexibility, and the number average molecular weight (Mn) is preferably 1,000-1,000,000, more preferably 5,000-9,00,000. The number average molecular weight (Mn) is the number average molecular weight of polystyrene conversion measured using GPC (gel permeation chromatography).

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

The glass transition temperature (Tg) of the resin whose glass transition temperature (Tg) is 25°C or lower is 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 higher. Also, among the 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.

Component (A) preferably has a functional group capable of reacting with component (B) from the viewpoint of improving the mechanical strength of the cured product. Moreover, the functional group which can react with (B) component also includes the functional group which appears by heating, for example.

In a preferred embodiment, the functional group that can react with component (B) is, for example, a group formed by hydroxyl group, carboxyl group, acid anhydride group, phenolic hydroxyl group, epoxy group, isocyanate group and urethane group More than one functional group selected; among them, the functional group is preferably, for example, hydroxyl group, acid anhydride group, phenolic hydroxyl group, epoxy group, isocyanate group and carbamate group, and hydroxyl group, acid anhydride group , phenolic hydroxyl group, and epoxy group are preferred, and phenolic hydroxyl group is particularly preferred.

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

Here, 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. In the butadiene structure, part or all of it can be hydrogenated. Here, the "resin containing a hydrogenated polybutadiene skeleton" means a resin in which at least a 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 from 1,000 to 100,000, more preferably from 5,000 to 50,000, more preferably from 7,500 to 30,000, most preferably from 10,000 to 15,000. However, the number average molecular weight (Mn) of resin is the number average molecular weight of polystyrene conversion measured using GPC (gel permeation chromatography).

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

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

Also, in another preferred embodiment of the component (A), for example, a resin having an imide structure can be used. Resins having an imide structure, for example, hydroxyl-terminated polybutadiene, diisocyanate compounds, and linear polyimides using tetrabasic anhydrides as raw materials (JP-A-2006-37083, International Publication No. 2008/153208 No. recorded polyimide) and so on. The polyimide resin has a polybutadiene structure content of preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, reference may be made to the records in JP-A-2006-37083 and International Publication No. 2008/153208, which are also incorporated into the description of this specification.

(A) A preferable one Embodiment of a component is an isoprene resin. Specific examples of the isoprene resin include, for example, "KL-610" and "KL-613" manufactured by Kuraray Corporation. Here, "isoprene resin" means a resin containing a polyisoprene structure, and in these resins, the polyisoprene structure may be included in the main chain or in the side chain.

Moreover, a preferable one Embodiment of (A) component is a carbonate resin. Carbonate resins, preferably carbonate resins with a glass transition temperature below 25°C, are also made of carbonate resins containing hydroxyl groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, and carbonic acid resins containing acid anhydride groups. 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, and 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 equivalent weight of the functional group 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 carbonate resins include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., "C-1090", "C-2090" and "C-3090" (polycarbonate) manufactured by Kuraray Co., Ltd. Carbonate diol), etc.

Also, hydroxyl-terminated polycarbonates, diisocyanate compounds, and linear polyimides using tetrabasic anhydrides as raw materials can also be used. The content rate of the polycarbonate structure of this polyimide resin becomes like this. Preferably it is 60 mass % - 95 mass %, More preferably, it is 75 mass % - 85 mass %. For details of the polyimide resin, reference may be made to the records in International Publication No. 2016/129541, which are also incorporated into this description.

Another preferred embodiment of the component (A) is an acrylic resin. Acrylic resins are preferably acrylic resins with a glass transition temperature (Tg) of 25°C or less, and acrylic resins containing hydroxyl groups, acrylic resins containing phenolic hydroxyl groups, acrylic resins containing carboxyl groups, and acrylic resins containing anhydride groups. 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 from 10,000 to 1,000,000, more preferably from 30,000 to 900,000. Here, the number average molecular weight (Mn) of resin is the number average molecular weight of polystyrene conversion measured using GPC (gel permeation chromatography).

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

Specific examples of acrylic resins include DENSAIRENI "SG-70L", "SG-708-6", "WS-023", "SG-700AS", and "SG-280TEA" (carboxyl group-containing acrylates) manufactured by Nagase Chemical Co., Ltd. Copolymer resin, acid value 5-34mgKOH/g, weight average molecular weight 400,000-900,000, Tg-30-5°C), "SG-80H", "SG-80H-3", "SG-P3" (contains Epoxy-based acrylate copolymer resin, epoxy equivalent 4761-14285g/eq, weight average molecular weight 350,000-850,000, Tg 11-12°C), "SG-600TEA", "SG-790" (containing hydroxyl Acrylate copolymer resin, hydroxyl value 20-40 mgKOH/g, weight-average molecular weight 500,000-1.2 million, Tg-37-32°C), Negami Kogyo Co., Ltd. "ME-2000", "W-116.3" (contains Carboxyl acrylate copolymer resin), "W-197C" (hydroxyl-containing acrylate copolymer resin), "KG-25", "KG-3000" (epoxy-containing acrylate copolymer resin), etc.

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

Specific examples of silicone resins include "SMP-2006", "SMP-2003PGMEA", and "SMP-5005PGMEA" manufactured by Shin-Etsu Polysiloxane Co., Ltd., amino-terminated polysiloxane, using tetrabasic anhydride as a raw material Linear polyimide (International Publication No. 2010/053185), etc. Here, "siloxane resin" means a resin containing a polysiloxane structure, and 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 Fiber Co., Ltd., "YX-7180" manufactured by Mitsubishi Chemical Corporation (an alkylene-containing group having an ether bond). structural resin), etc. DIC Corporation "EXA-4850-150", "EXA-4816", "EXA-4822", ADEKA Corporation "EP-4000", "EP-4003", "EP-4010", and "EP-4011", new "BEO-60E" and "BPO-20E" manufactured by Nippon Chemical Co., Ltd., "YL7175" and "YL7410" manufactured by Mitsubishi Chemical Corporation, etc. Here, "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 may be included 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, and in these resins, the polyisobutylene structure may be included in the main chain or in the side chain.

Also, another preferred embodiment of the component (A) is, for example, acrylic rubber particles, polyamide microparticles, polysiloxane particles, and the like. Specific examples of acrylic rubber particles, such as acrylonitrile butadiene rubber, butadiene rubber, acrylic rubber and other resins that exhibit rubber elasticity, are chemically cross-linked to form fine particles of resin that are insoluble in organic solvents and will 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 Corporation), 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), SP500 (manufactured by Toray Corporation), or the like.

The content of component (A) in the resin composition is when the non-volatile component (resin component) of the resin composition after excluding components (C) and (G) is 100% by mass from the viewpoint of imparting flexibility , preferably less than 65% by mass, more preferably less than 60% by mass, particularly preferably less than 55% by mass, most preferably less than 50% by mass. Also, the lower limit is preferably at least 10% by mass, more preferably at least 15% by mass, particularly preferably at least 20% by mass, most preferably at least 25% by mass.

<(B) Epoxy resin> The resin composition of the present invention contains an epoxy resin as the (B) component. The component (B) is preferably an epoxy resin having an aromatic structure from the viewpoint of enhancing the effect of the present invention. Aromatic structure generally refers to a chemical structure defined as aromatic, and also includes polycyclic aromatic and aromatic heterocycles.

Epoxy resins, for example, bisphenol A type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclic Pentadiene type epoxy resin, triphenol type epoxy resin, naphthol-novolak type epoxy resin, phenol-novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type ring Oxygen resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin with aromatic structure, glycidyl ester type epoxy resin with aromatic structure, cresol-novolak type epoxy resin Resin, biphenyl type epoxy resin, linear aliphatic epoxy resin with aromatic structure, epoxy resin with butadiene structure with aromatic structure, alicyclic epoxy resin with aromatic structure, heterogeneous Cyclic epoxy resin, spiro ring-containing epoxy resin with aromatic structure, cyclohexanedimethanol epoxy resin with aromatic structure, pernaphthylether epoxy resin, trimethylol with aromatic structure Base type epoxy resin, tetraphenylethane type epoxy resin, aminophenol type epoxy resin, etc. Epoxy resins may be used alone or in combination of two or more. (B) The 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 having two or more epoxy groups in one molecule. Also, when the non-volatile content of the epoxy resin is 100% by mass, at least 50% by mass of the epoxy resin having two or more epoxy groups in one molecule is preferably. Among them, epoxy resins that contain 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 three or more 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 resins") 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 product of the resin composition can also be improved.

Liquid epoxy resins, 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 , Glycidylamine type epoxy resin with aromatic structure, phenol-novolak type epoxy resin, alicyclic epoxy resin with ester skeleton with aromatic structure, cyclohexanedimethanol 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 resins, aminophenol epoxy resins and naphthalene epoxy resins are preferred, and bisphenol A epoxy resins, bisphenol F epoxy resins, and aminophenol epoxy resins are more preferred. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation, "828US" and "jER828EL" (bisphenol A-type epoxy resins) manufactured by Mitsubishi Chemical Corporation. Oxygen resin), "jER806", "jER807" (bisphenol F epoxy resin), "jER152" (phenol-novolac epoxy resin), "630" (aminophenol epoxy resin), "630LSD "(glycidylamine type epoxy resin), "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "EX -721" (glycidyl ester type epoxy resin), "CELLOXIDE 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by DAICEL, "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane), "YX7400" (high resilience epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used individually by 1 type, and may use it in combination of 2 or more types.

Solid epoxy resins such as bixylenol type epoxy resins, naphthalene type 4-functional epoxy resins, cresol-novolak type epoxy resins, dicyclopentadiene type epoxy resins, triphenol type epoxy resins Resin, naphthol type epoxy resin, biphenyl type epoxy resin, pernathyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenyl ethyl ether Alkane type epoxy resin is the best, and bixylenol type epoxy resin, naphthalene type 4-functional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and xylenyl ether type epoxy resin are more suitable. Preferably, dicresol-type epoxy resin, naphthalene-type 4-functional epoxy resin, pernaphthylether-type epoxy resin, and biphenyl-type epoxy resin are more preferable. 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-Novolak 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" (pernaphthyl ether type Epoxy resin), "EPPN-502H" (triphenol type epoxy resin), "NC7000L" (naphthol-novolak 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 Sumikin 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 Corporation (anthracene-type epoxy resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" manufactured by Mitsubishi Chemical Corporation (anthracene-type epoxy resin), "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), "157S70" (bisphenol-novolac type epoxy resin), "YX4000HK" manufactured by Mitsubishi Chemical Corporation (dicresol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100" manufactured by Osaka Gas Chemical Co., Ltd., "CG-500", "YL7800" manufactured by Mitsubishi Chemical Co., Ltd. type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These may be used individually by 1 type, and may use it in combination of 2 or more types.

(B) In the component, when liquid epoxy resin and solid epoxy resin are used together, the amount ratio of these (solid epoxy resin: liquid epoxy resin) is 1 when the mass ratio is used as the basis. : The range of 0.1～1:15 is preferable. When the amount ratio of the liquid epoxy resin to the solid epoxy resin is within this range, i) when used in the form of a resin sheet, it can have appropriate adhesiveness, and ii) when used in the form of a resin sheet, it can be fully Part of the flexibility can improve the handleability, and iii) can obtain a hardened product with sufficient breaking strength and the like. From the viewpoint of the effects of the above i) to iii), the ratio of liquid epoxy resin to solid epoxy resin (solid epoxy resin: liquid epoxy resin) is based on the mass ratio of 1 : The range of 0.3-1:10 is better, and the range of 1:0.6-1:8 is more preferable.

The content of the epoxy resin in the resin composition can be used to obtain an insulating layer with good mechanical strength and insulation reliability. When the non-volatile content in the resin composition is set to 100% by mass, it is preferably 1 mass % % or more, more preferably 2 mass % or more, and 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, but it is preferably 10% by mass or less, more preferably 8% by mass or less, particularly preferably 6% by mass or less.

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

The epoxy equivalent of the epoxy resin is preferably 50-5000, more preferably 50-3000, particularly preferably 80-2000, most preferably 110-1000. When it is within this range, it is possible to obtain an insulating layer having a sufficient crosslink density with the cured product and having a smaller surface roughness. In addition, the epoxy equivalent can be measured according to the provisions of JIS K7236, and it is the mass of resin containing 1 equivalent of epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100-5000, more preferably 250-3000, and most preferably 400-1500. Here, the weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) method.

<(C) Thermally conductive filler> The resin composition of the present invention contains (C) thermally conductive filler. Note that, in this specification, the thermally conductive filler means an inorganic filler having a thermal conductivity of 20 W/m·K or higher.

The material of the component (C) is not particularly limited as long as the thermal conductivity is within the above range. Materials containing component (C), such as alumina, aluminum nitride, boron nitride, silicon carbide, etc. Among these, alumina is particularly preferable. (C) Components may be used alone or in combination of two or more. Moreover, it is also possible to use in combination of 2 or more types of same materials.

The average particle size of the component (C) is preferably 5 μm or less, more preferably 4 μm or less, and is particularly preferably 3 μm or less; more 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, the particle size distribution of the inorganic filler is produced on a volume basis using a laser diffraction scattering particle size distribution measuring device, and the median diameter thereof is used as the average particle size. For the determination of samples, it is better to use ultrasonic wave to disperse component (C) in water. As the laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba Manufacturing Co., Ltd., "SALD2200" manufactured by Shimadzu Corporation, etc. can be used. Specifically, for example, it can be measured according to the method described in <Measurement of Average Particle Size of Thermally Conductive Filler> below.

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 to 10m ² /g, more preferably 0.5m ² /g to 5m ² /g. (C) The specific surface area of the component can be measured using the nitrogen BET method. Specifically, for example, the measurement can be performed using an automatic specific surface area measuring device, and for the automatic specific surface area measuring device, for example, "Macsorb HM-1210" manufactured by MOUNTECH, etc. can be used. Specifically, for example, it can be measured by the method described in <The measurement of the specific surface area of a thermally conductive filler> mentioned later.

(C) component, from the viewpoint of improving moisture resistance and dispersibility, one or more aminosilane-based coupling agents, epoxy-silane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, Surface treatment agents such as alkoxysilane compounds, organic silazane compounds, and titanate-based coupling agents. Commercially available surface treatment agents, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyl Trimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxy base silane), Shin-Etsu Chemical Co., Ltd. "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy-type silane coupling agent), etc. Among them, from the viewpoint of lowering the melt viscosity and improving laminarity, component (C) is preferably surface-treated with an aminosilane-based coupling agent, and N-phenyl-3-aminopropyltrimethoxy Silane, N-phenyl-3-aminooctyltrimethoxysilane, it is better to use N-phenyl-3-aminoalkyltrimethoxysilane for surface treatment, and use N-phenyl-3- Aminooctyltrimethoxysilane for surface treatment is preferred.

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

<(D) Active ester hardener> The resin composition of the present invention contains (D) active ester hardener. There are no special restrictions on active ester hardeners. Generally, there are more than 2 phenolic esters, thiophenolic esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds with high reactivity in one molecule. Ester-based compounds are preferred users. The active ester hardener is preferably obtained by condensation reaction of carboxylic acid compound and/or thiocarboxylic acid compound with hydroxyl compound and/or thiol compound. In particular, from the viewpoint of improving heat resistance, active ester hardeners made from carboxylic acid compounds and hydroxyl compounds are preferred, and active ester hardeners made from carboxylic acid compounds and phenolic compounds and/or naphthol compounds are 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. Phenol compounds or naphthol compounds such as hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 ,6-Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, glucinol, dicyclopentadiene-type diphenol compounds, phenol-phenolic novolac Varnish etc. Here, the "dicyclopentadiene-type diphenol compound" means a diphenol compound obtained by condensing 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 acetylated phenol-novolac, an active ester compound containing a phenol-novolak Active ester compounds of benzoyl compounds are preferred, among which active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" means a bivalent structure formed of phenylene-dicyclopentylene-phenylene.

As the active ester compound, for example, active ester compounds disclosed in JP-A-2004-277460 and JP-A-2013-40270 can be used, or commercially available active ester compounds can be used. Among the commercially available active ester hardeners, active ester compounds containing dicyclopentadiene-type diphenol structures, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "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); "DC808" (manufactured by Mitsubishi Chemical Corporation), active ester compound containing phenol-novolak benzoyl compound such as "YLH1026" (manufactured by Mitsubishi Chemical Corporation); active ester hardener of phenol-novolac acetyl compound such as " DC808" (manufactured by Mitsubishi Chemical Corporation), active ester hardeners of benzoyl compounds of phenol-novolac such as "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) manufactured by the company), "EXB9050L-62M" manufactured by DIC Corporation (phosphorous atom-containing active ester compound), etc.

The content of the component (D) is preferably at most 5% by mass, more preferably at most 3% by mass, and most preferably at most 2% by mass, when the non-volatile content in the resin composition is 100% by mass. Also, the lower limit is not particularly limited, but generally it is preferably at least 0.1% by mass, more preferably at least 0.5% by mass. When the content of the component (D) is within this range, thermal conductivity and peel strength can be improved.

系硬化劑、氰酸酯酯系硬化劑，及碳二醯亞胺系硬化劑等。硬化劑可單獨使用1種亦可，或將2種以上合併使用亦可。(D)成份，以由酚系硬化劑、萘酚系硬化劑，及氰酸酯酯系硬化劑所選出之1種以上為佳，以由酚系硬化劑所選出之1種以上為較佳。<(E) Curing agent> In addition to (D) component, the resin composition of this invention may further contain (E) hardening agent. In addition, the (E) component mentioned here does not contain (D) active ester hardener. (E) The curing agent is not particularly limited as long as it has the function of curing the resin such as the (B) component, for example, a phenolic curing agent, a naphthol-based curing agent, a benzoxan

Hardeners, cyanate ester hardeners, carbodiimide hardeners, etc. A hardening agent may be used individually by 1 type, or may use it in combination of 2 or more types. Component (D) is preferably at least one selected from phenolic hardeners, naphthol-based hardeners, and cyanate ester-based hardeners, preferably at least one selected from phenolic hardeners .

骨架之酚系硬化劑為較佳。其中，就耐熱性、耐水性，及可高度滿足與配線層的密著性之觀點，以使用含有三

骨架之酚-酚醛清漆硬化劑為佳。The phenolic hardener and the naphthol hardener are preferably phenolic hardeners having a novolac structure or naphthol hardeners with a novolak structure from the viewpoint of heat resistance and water resistance. Also, from the viewpoint of adhesion to the wiring layer, nitrogen-containing phenolic hardeners are preferred, containing three

Skeleton phenolic hardener is preferred. Among them, from the standpoint of heat resistance, water resistance, and high adhesion to the wiring layer, the use of three

Skeleton phenol-novolac hardener is preferred.

Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "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" and "GDP-6115H" manufactured by Qunying Chemical Co., Ltd., etc.

系硬化劑之具體例如，昭和高分子公司製之「HFB2006M」、四國化成工業公司製之「P-d」、「F-a」等。Benzox

Specific examples of the curing agent include "HFB2006M" manufactured by Showa High Polymer Co., Ltd., "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd., and the like.

化而得之預聚物等。氰酸酯酯系硬化劑之具體例如，LONZAJAPAN公司製之「PT30」及「PT60」(任一者皆為酚-酚醛清漆型多官能氰酸酯樹脂)、「BA230」、「BA230S75」(雙酚A二氰酸酯的一部份或全部經三

化而形成三聚物的預聚物)等。Cyanate ester-based hardeners, such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'- 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 of cyanate phenyl-1-(methylethylene)benzene, bis(4-cyanate phenyl)sulfide, and bis(4-cyanate phenyl)ether Polyfunctional cyanate resins derived from resins, phenol-novolaks and cresol-novolacs, etc., and these cyanate resins are partially three

The resulting prepolymers, etc. Specific examples of cyanate ester-based hardeners include "PT30" and "PT60" (both of which are phenol-novolac type polyfunctional cyanate resins), "BA230" and "BA230S75" (bis Part or all of phenol A dicyanate

to form prepolymers of terpolymers) and the like.

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

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

<(F) Hardening Accelerator> The resin composition of the present invention contains (F) a hardening accelerator. The hardening accelerator includes, for example, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, metal-based hardening accelerators, and the like. 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. The hardening accelerator may be used alone or in combination of two or more.

Phosphorus-based hardening accelerators, such as triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylboride, n-butylphosphonium tetraphenylboride, tetrabutylphosphonium decanoate , (4-tolyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc., and triphenylphosphine, tetrabutylphosphonium decyl Salt is better.

Amine-based hardening accelerators, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-ginseng (dimethylaminomethyl) Phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., and 4-dimethylaminopyridine, 1,8-diazabicyclo(5,4,0)-deca Monoene is preferred.

、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三

、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三

、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三

異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-4,5-二羥甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑、2,3-二氫-1H-吡咯[1,2-a]苯併咪唑、1-十二烷基-2-甲基-3-苄基咪唑鹽氯化物、2-甲基咪唑啉、2-苯基咪唑啉等的咪唑化合物及咪唑化合物與環氧樹脂之加成物等，又以2-乙基-4-甲基咪唑、1-苄基-2-苯基咪唑為佳。Imidazole-based hardening accelerators, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitic acid Esters, 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-dimethylolimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methyl Imidazole compounds such as base imidazoline, 2-phenylimidazoline and the adducts of imidazole compounds and epoxy resins, etc., and 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole better.

As the imidazole-based hardening accelerator, commercially available products such as "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc. can also be used.

Guanidine-based hardening accelerators, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dicyandiamide, 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-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., and Preferred are dicyanodiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

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

In the resin composition, when the component (F) is contained, the content of the component (F) in the resin composition is not particularly limited, and when the non-volatile content in the resin composition is 100% by mass, it is 0.01% by mass ~1% by mass is preferable.

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

The average particle size of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, particularly preferably 2.2 μm or less, from the viewpoint of producing an insulating layer with high line embedding and low surface roughness. Preferably, it is 2 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably at least 0.01 μm, more preferably at least 0.05 μm, and particularly preferably at least 0.1 μm. The average particle size of the inorganic filler can be measured in the same way as component (C). Commercially available inorganic fillers having these average particle diameters include, for example, "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by ADMATECHS, "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd., "SILFILE NSS-3N", "SILFILE NSS-4N", "SILFILE NSS-5N", "SC2500SQ", "SO-C6", "SO-C4", "SO-C2", " SO-C1", etc.

For inorganic fillers, from the viewpoint of improving moisture resistance and dispersibility, one or more aminosilane-based coupling agents, epoxy-silane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxy It is better to treat with surface treatment agents such as silane compounds, organic silazane compounds, and titanate-based coupling agents. Specific commercial products of the surface treatment agent are as described above.

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

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

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

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

<(I) Arbitrary additives> The resin composition may contain other additives, such as organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds, as well as binders, additives, etc., if necessary. Adhesives, defoamers, leveling agents, adhesion imparting agents, resin additives such as coloring agents, etc.

<Physical properties of the resin composition> The resin composition of the present invention is hardened by heating at 180°C for 30 minutes and then at 180°C for 60 minutes. The characteristic of excellent peel strength between metal layers. 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, it can be plated to form a metal layer on the roughened surface of the cured product after the roughening treatment. After 10 minutes of heat treatment, it can show the characteristics of excellent peel strength between the hardened product and the metal layer. The peel strength is preferably at least 0.4 kgf/cm, more preferably at least 0.45 kgf/cm, and most preferably at least 0.5 kgf/cm. 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, and the like. The evaluation of peel strength can be carried out according to the method described in <Measurement and Evaluation of Tensile Peel Strength (Peel Strength) of Metal Layer> below. The metal layer is preferably a metal layer containing copper, more preferably a metal layer formed by plating.

The cured product of the resin composition of the present invention after thermal curing 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 at least 1.5 W/m·K, more preferably at least 1.8 W/m·K, and most preferably at least 2.0 W/m·K. 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. The thermal conductivity can be evaluated by the method described in <Measurement of Thermal Conductivity of Cured Material> below.

The cured product of the resin composition of the present invention after thermal curing at 180°C for 90 minutes exhibits a characteristic of low elastic modulus at 23°C. That is, an insulating layer with a low modulus of elasticity. The modulus of elasticity is preferably at most 25 GPa, more preferably at most 20 GPa, most preferably at most 15 GPa. The lower limit is 0.1 GPa or more. The modulus of elasticity can be measured according to the method described in <Measurement of modulus of elasticity> described later.

The cured product of the resin composition of the present invention after being thermally cured at 100°C for 30 minutes and then at 180°C for 30 minutes shows the characteristic of low warpage. That is, an insulating layer with a low amount of warpage. It is preferable that the average value of the respective warping amounts of the four corners is 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 the characteristic of low melt viscosity. In this way, the laminarity 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 at least 500 poise, more preferably at least 1000 poise, particularly preferably at least 1500 poise; preferably at most 8500 poise, more preferably at most 8000 poise, most preferably at most 7500 poise, or at most 7000 poise. Melt viscosity can be measured according to the method described in <Measurement of Melt Viscosity> 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 suitable for use as a resin composition for forming an insulating layer of a semiconductor chip package (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 the insulating layer of the circuit board) is more suitable for use as a resin composition for forming an interlayer insulating layer on a substrate with a conductive layer formed by plating (a circuit board with a conductive layer formed by plating, that is, A resin composition for an interlayer insulating layer of a circuit substrate formed by a semi-additive process). In addition, it is also suitable for use as a resin composition for sealing a semiconductor chip (resin composition for semiconductor chip sealing), and a resin composition for forming wiring on a semiconductor chip (resin composition for forming semiconductor chip wiring).

[Resin sheet] The resin sheet of the present invention is a resin composition layer comprising a support and the resin composition of the present invention provided on the support.

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 from the viewpoint of thinning. 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, and the like.

The support body is, for example, a film, metal foil, release paper, etc. formed of plastic materials, preferably a film or metal foil formed of plastic materials.

When the support is made of a film obtained from a plastic material, 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 polyesters, polycarbonate (hereinafter also referred to as "PC"), acrylates such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether Sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthyl ester are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When metal foil is used as the support, the metal foil, for example, copper foil, aluminum foil, etc., is preferably copper foil. Copper foil can be formed of a single metal of copper, or an alloy of copper and other metals (such as 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.

Also, as the support body, a support body with a release layer having a release layer on the surface to which the resin composition layers are connected can be used. The release agent used as the release layer of the support with the release layer, for example, selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin More than 1 type of release agent. The support body with the release layer can also use commercially available products, for example, the PET film with the release layer of the alkyd resin release agent as the main component, "SK-1" and "AL -5", "AL-7", "RUMINA T60" manufactured by Toray Corporation, "PUREX" manufactured by Teijin Corporation, "YUNIPIRE" manufactured by UNITIKA Corporation, etc.

The thickness of the support body is not particularly limited, and generally it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. Moreover, when using the support body with a release layer, it is preferable that the whole thickness of the support body with a release layer falls within the said range.

For resin flakes, for example, a resin coating can be produced by dissolving a resin composition in an organic solvent, and then coating the resin coating on a support using a slit coater or a compression mold method, and then drying it to form a resin sheet. Manufactured in the form of layers.

Organic solvents such as acetone, ketones such as methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carboxylate Acetates such as benzyl acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide Amide solvents such as amine (DMAc) and N-methylpyrrolidone, etc. An organic solvent may be used individually by 1 type, or may use it in combination of 2 or more types.

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

In the resin sheet, on the side not connected to the support of the resin composition layer (that is, the side opposite to the support), a protective film can be further laminated in conjunction with the support. The thickness of the protective film is not particularly limited, for example, 1 μm˜40 μm. By laminating a protective film, it is possible to prevent impurities, etc. from adhering to or damaging the surface of the resin composition layer. Resin flakes can be rolled up and stored in the form of a roll. When the resin sheet has a protective film, it can be used after peeling off the protective film.

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

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

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

The sheet-like fiber substrate used in the prepreg is not particularly limited, and glass fiber cloth, aramid non-woven fabric, liquid crystal polymer non-woven fabric, etc. commonly used as prepreg substrates can generally be used. From the viewpoint of thinning, the thickness of the flaky fibrous substrate is preferably at most 900 μm, more preferably at most 800 μm, particularly preferably at most 700 μm, most preferably at most 600 μm. The lower limit of the thickness of the flake-shaped fibrous base material is not particularly limited, but it is usually 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

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

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

[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) preparing a base material, and the step of a base material with a wiring layer having a wiring layer disposed on at least one side of the base material, (2) The step of laminating the resin sheet of the present invention on the base material with the wiring layer in such a way that the wiring layer is embedded in the resin composition layer, and forming an insulating layer by thermosetting, (3) placing the wiring layer between the layers Steps to form a connection. Moreover, in the manufacturing method of a circuit board, (4) the process of removing a base material may also be included.

In step (3), as long as the wiring layer can be connected between the layers, there is no special limitation, and the step of forming the wiring layer is formed by forming a via hole in the insulating layer, and the insulating layer Grinding or grinding, any one of the step of exposing the wiring layer is preferable.

<Step (1)> Step (1) is a step of preparing a substrate and a substrate with a wiring layer having a wiring layer provided on at least one side of the substrate. Usually, the base material with the wiring layer has a first metal layer and a second metal layer as a part of the base material in sequence on both sides of the base material, and a metal layer on the base material side of the second metal layer The wiring layer is formed on the opposite side. Specifically, a dry film (photosensitive resist film) is laminated on a base material, exposed and developed under specific conditions using a photomask, and a patterned dry film is formed. The patterned dry film after development is used as a plating mask, and after the wiring layer is formed by electrolytic plating, the patterned dry film is peeled off. Moreover, it is not necessary to have a 1st metal layer and a 2nd metal layer.

Substrates, such as glass epoxy substrates, metal substrates (stainless steel or cold-rolled steel plate (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene oxide substrates, etc., It can also form a metal layer such as copper foil on the surface of the substrate. In addition, a metal layer such as a peelable first metal layer and a second metal layer (for example, Mitsui Kinzoku's ultra-thin copper foil with carrier, trade name "Micro Thin") can 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, a dry film of novolac resin, acrylic resin, or the like can be used. A commercial item can also be used for a dry film.

The lamination conditions of the base material and the dry film are the same as the lamination conditions in the method of embedding 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 to form the desired pattern on the dry film can be used to expose and develop according to specific conditions.

The ratio of the line (line width)/space (width between lines) of the wiring layer is not particularly limited, preferably below 20/20μm (that is, the spacing is below 40μm), more preferably below 10/10μm, especially Preferably it is 5/5 μm or less, particularly preferably 1/1 μm or less, most preferably 0.5/0.5 μm or more. It is not necessary for all the pitches to be the same in all the 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 use the dry film formed with the desired pattern as a plating mask, and implement it according to the plating method.

The conductor material used in the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer is composed of one 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 metal. The wiring layer can be a single metal layer or an alloy layer. The alloy layer is, 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) formed by etc. Among them, from the viewpoint of the extensiveness, cost, and ease of pattern formation of the wiring layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a nickel-chromium alloy , Copper-nickel alloy, copper-titanium alloy alloy layer is preferred, single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloy alloy layer is preferred , a single metal layer of copper is better.

The thickness of the wiring layer 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, depending on the desired wiring board design. In step (3), when using the step of grinding or grinding the insulating layer to expose the wiring layer so that the wiring layer is connected between the layers, the thickness of the wiring connected between the layers is preferably different from that of the unconnected wiring. . 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 support) is preferably not less than 2 μm and not more than 100 μm, depending on the desired design of the wiring board. Moreover, the wiring connected between layers may also be in a convex shape.

After the wiring layer is formed, the dry film is peeled off. The stripping method of the dry film can be carried out by using an alkaline stripping solution such as sodium hydroxide solution, for example. If necessary, unnecessary wiring patterns can be removed by etching or the like to form desired wiring patterns. The distance between the formed wiring layers is as described above.

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

The method of laminating the wiring layer and the resin sheet can be performed by, for example, heating and pressing the resin sheet to the wiring layer from the support side after removing the protective film of the resin sheet. A member for heat-bonding a resin sheet to a wiring layer (hereinafter also referred to as “heat-bonding member”) is, 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 a heat 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 unevenness of the wiring layer.

The lamination method of the wiring layer and the resin sheet can be implemented by vacuum lamination 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, more preferably in the range of 0.29MPa to 1.47 In the range of MPa, the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions with a pressure of 13 hPa or less.

After lamination, the laminated resin sheet is 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 above-mentioned heating and pressing conditions for lamination. In addition, the lamination and smoothing treatment can be continuously performed using the above-mentioned commercially available vacuum laminator.

After the resin composition layer is laminated on the substrate with the wiring layer embedded in the wiring layer, the resin composition layer can be thermally cured to form an insulating layer. For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, etc., and the general curing temperature is in the range of 120° C. to 240° C., and the curing time is in the range of 5 minutes to 120 minutes. Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature.

The support body of the resin sheet may be laminated on the substrate with the wiring layer, and then peeled off after thermosetting, or the support may be peeled off before laminating the resin sheet on the substrate with the wiring layer. Moreover, before the roughening process process mentioned later, you may peel a support body.

After the resin composition layer is thermally cured to form the insulating layer, the surface of the insulating layer may also be polished. The grinding method is not particularly limited, and known methods can be used for grinding, for example, using a flat grinding disc to grind the surface of the insulating layer.

<Step (3)> Step (3) is a step of connecting the wiring layers between layers. The detailed content is a step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layer between layers. Or the step of grinding or grinding the insulating layer to expose the wiring layer so that the wiring layer is connected between layers. The conductor layer may also be called a wiring layer.

When using the step of forming a through hole in the insulating layer, forming a conductive layer, and forming a connection between 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 carbon dioxide laser, a YAG laser, an excimer laser, or the like. In detail, laser irradiation is performed from the support body surface side of the resin sheet to penetrate the support body and the insulating layer to expose the wiring layer and form via holes.

The conditions of the laser irradiation are not particularly limited, and the laser irradiation can be carried out using any appropriate steps according to the usual method in accordance with the selected means.

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

After the through-holes are formed, a so-called desmear step is performed as a step of removing smudges in the through-holes. When the conductive layer is formed using the plating step described later, wet desmear treatment can be performed on the through hole, for example, and dry desmear treatment such as a plasma treatment step can be performed when the conductive layer is formed by the sputtering step. step. In addition, in the stain removal step, the roughening treatment step may also be performed concurrently.

Before forming the conductor layer, roughening treatment may be performed on the via hole and the insulating layer. For the roughening treatment, generally known procedures and conditions can be employed. Examples of dry roughening treatment include, for example, plasma treatment, etc. Examples of wet roughening treatment, for example, sequentially use swelling treatment using a swelling solution, roughening treatment using an oxidizing agent, and intermediate treatment using a neutralizing solution. and processing methods.

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

After the via hole is formed, the conductor layer is formed. The conductor material constituting the conductor layer is not particularly limited, and the conductor layer can be formed by any appropriate conventionally known method such as plating, sputtering, and vapor deposition, and is preferably formed by plating. A preferred embodiment, for example, can be plated on the surface of the insulating layer by using known techniques such as semi-additive process (Semi-additive Process) and full-additive process to form a desired wiring pattern. the conductor layer. Among them, the semi-additive method is preferred. In addition, in the resin sheet, when the support body is a metal foil, a conventionally known technique such as a subtractive process can be used to form a conductor layer having a desired wiring pattern. The conductor layer may be a single layer structure, or a multilayer structure obtained by laminating two or more single metal layers or alloy layers formed of different kinds of metals or alloys.

The method of forming using plating is, specifically, forming a plating seed layer on the surface of an insulating layer using electroless plating. Next, on the formed plating seed layer, a part of the plating seed layer is exposed to form a mask pattern according to the expected wiring pattern. On the exposed plating seed layer, an electrolytic plating layer is formed by electrolytic plating. At this time, at the same time as forming the electrolytic plating layer, a buried via (filled via) in which a via hole is buried using electrolytic plating may be formed. After forming the electrolytic plating layer, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching etc., and the conductor layer which has a desired wiring pattern is formed. Also, when forming the conductor layer, the dry film used for forming the mask pattern is the same as the dry film described above.

The conductor layer includes, for example, not only linear wiring but also electrode pads (lands) on which external terminals are mounted. In addition, the conductive layer may be composed only of electrode pads.

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

When using the step of grinding or grinding the insulating layer to expose the wiring layer to form a connection between the wiring layer and the wiring layer, as long as the grinding or grinding method of the insulating layer can expose the wiring layer and make the ground or ground surface horizontal, It is not particularly limited, and conventionally known grinding methods or grinding methods can be used, for example, a chemical mechanical polishing method using a chemical mechanical polishing device, a mechanical polishing method such as a mirror surface, a plane grinding method using rotary abrasive grains, and the like. 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, and can be performed on a stain removal step, a roughening treatment step, or the formation of a conductor layer. Also, 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 substrate to form the circuit board of the present invention. The method of removing the substrate is not particularly limited. In a preferred embodiment, at the interface between the first and second metal layers, the circuit board is peeled off from the base material, and then the second metal layer is etched away using, for example, an aqueous copper chloride solution. If necessary, the substrate can also be peeled off in a state where the conductor layer is protected by the protective film.

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

[Semiconductor Chip Package] 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 above-mentioned circuit board. It can be used to make a semiconductor chip package by connecting it to the semiconductor chip on the above-mentioned circuit substrate.

As long as the terminal electrodes of the semiconductor chip can be electrically connected to 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 via an insulating adhesive.

In a preferred embodiment, the semiconductor wafer is pressed against the circuit board. 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°C. The range of seconds (preferably 5 seconds to 30 seconds).

In addition, another preferred embodiment is that the semiconductor chip is connected by reflow on the circuit board. 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 to obtain a semiconductor chip package. The method of filling with an underfill material can be implemented using a well-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, a semiconductor chip package (Fan-out type WLP) as shown in an example in FIG. 1 . A semiconductor chip package (Fan-out type WLP) 100 shown as an example 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 so as to cover the semiconductor chip 110 and the periphery of the semiconductor chip 110, and a rewiring formation layer on the surface opposite to the side of the sealing layer covering the semiconductor chip 110. (insulation layer) 130 , conductor layer (rewiring layer) 140 , solder resist layer 150 , and bump 160 . These semiconductor chip packaging manufacturing methods include: (A) the step of laminating a pre-fixed film on the base material, (B) the step of pre-fixing the semiconductor chip on the pre-fixed film, (C) applying the resin sheet of the present invention The resin composition layer is laminated on the semiconductor wafer, or the step of coating the resin composition of the present invention on the semiconductor wafer, making it thermally hardened to form a sealing layer, (D) forming the base material and the pre-fixed film from the semiconductor wafer Wafer peeling step, (E) Step of forming a rewiring forming layer (insulating layer) on the surface where the substrate and pre-fixed film are peeled off from the semiconductor wafer, (F) Forming a conductor layer on the rewiring forming layer (insulating layer) (rewiring layer), and (G) a step of forming a solder resist layer on the conductor layer. In addition, the method for manufacturing a semiconductor chip package also includes (H) a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to form individual chips.

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

樹脂所形成之基板等。The material used as the substrate is not particularly limited. Substrates, for example, silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel plates (SPCC); epoxy resin infiltrated into glass fibers such as FR-4 substrates, etc., Substrate after thermal hardening treatment; bismaleimide three of BT resin

Substrates made of resin, etc.

The material of the pre-fixed film is not particularly limited as long as it can pre-fix the semiconductor wafer while peeling off the semiconductor wafer in the step (D) described later. As the pre-fixed film, commercially available ones can be used. Commercially available items include LIWA-α manufactured by Nitto Denko Co., Ltd., and the like.

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

<Step (C)> Step (C) is to laminate the resin composition layer of the resin sheet of the present invention on the semiconductor wafer, or apply the resin composition of the present invention to the semiconductor wafer, and heat-cure it And the step of forming the sealing layer. In the step (C), it is preferable to laminate the resin composition layer of the resin sheet on the semiconductor wafer and heat-cure to form the sealing layer.

The lamination method of the semiconductor wafer and the resin sheet can be carried out by, for example, heat-pressing the resin sheet to the semiconductor wafer from the support side after removing the protective film from the resin sheet. A member for thermally bonding a resin sheet to a semiconductor wafer (hereinafter, also referred to as “heat-pressing member”), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). Also, rather than directly pressurizing the resin sheet with a heat-pressing member, it is preferable to pressurize the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface irregularities of the semiconductor wafer.

In addition, the lamination method of the semiconductor wafer and the resin sheet can be carried out by vacuum lamination after the protective film is removed 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 the 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 the substrate and pre-fixed film from the semiconductor wafer. The method of peeling can be appropriately changed in accordance with the material of the pre-fixed film, for example, the method of peeling the pre-fixed film after heating, foaming (or expansion), and irradiating ultraviolet rays from the substrate side to reduce the thickness of the pre-fixed film. The method of peeling off due to the adhesive force, etc.

In the method of peeling off the pre-fixed film after heating, foaming (or expansion), the heating conditions are usually between 100° C. and 250° C. 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 pre-fixed film and peeling off, the irradiation amount of ultraviolet rays is usually 10mJ/cm ² to 1000mJ/cm ² .

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

The material that can form the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties when forming the rewiring formation layer (insulating layer). From the viewpoint of the ease of manufacturing semiconductor chip packages, Photosensitive resin and thermosetting resin are preferable. 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 forming the rewiring forming layer (insulating layer), via holes can be formed on the rewiring forming layer (insulating layer) for the purpose of forming an interlayer connection between the semiconductor chip and the conductor layer described later.

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

Active energy rays, for example, ultraviolet rays, visible light, electron rays, X-rays, etc., especially ultraviolet rays are preferred. The irradiation amount and irradiation time of ultraviolet rays can be appropriately changed according to the photosensitive resin. The exposure method can be a contact exposure method in which the mask pattern is adhered to the rewiring formation layer (insulating layer), and the mask pattern is not adhered to the rewiring formation layer (insulating layer). Any of the non-contact exposure methods for exposing with parallel rays may be used.

Next, the rewiring formation layer (insulating layer) is developed to remove the unexposed portion to form a via hole. For image development, either wet image development or dry image image may be used. As the developing solution used for wet development, a known developing solution can be used.

Developing methods include, for example, dipping, stirring, spraying, brushing, and scraping. From the viewpoint of resolution, stirring is preferred.

When the material for forming the rewiring formation layer (insulation 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 can be used better. Laser irradiation can be performed using any suitable laser processing machine whose light source is carbon dioxide laser, UV-YAG laser, excimer laser, or the like.

The conditions of the laser irradiation are not particularly limited, and the laser irradiation can be carried out using any appropriate steps according to the usual method in accordance with the selected means.

The shape of the through hole, when viewed from the extension direction, the shape of the opening is not particularly limited, and it is generally circular (slightly circular). The diameter of the top of the via hole (the diameter of the opening on the surface of the redistribution forming layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit is not particularly limited, but generally, it is preferably at least 10 μm, more preferably at least 15 μm, and most preferably at least 20 μm.

<Step (F)> Step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer). The method of forming a conductor layer on the rewiring formation layer (insulation layer) is the same as the method of forming a conductor layer after forming a through hole in the insulation layer in step (3) in the manufacturing method of the circuit board, and the preferred range is also the same. In addition, step (E) and step (F) can also be repeated, so that the conductor layer (rewiring layer) and the rewiring formation layer (insulating layer) are alternately laminated (stacked).

<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 the solder resist layer is insulating when it is formed. 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.

In addition, in the step (G), if necessary, bump processing for forming bumps may be performed. As the bump processing method, known methods such as solder balls and solder plating can be used. Also, in the bump processing, the method of forming the through hole can be carried out in the same way as step (E).

<Step (H)> In the manufacturing method of a semiconductor chip package, a step (H) other than steps (A) to (G) may be included. The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to form individual pieces.

The method of dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited, and known methods can be used.

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

[Semiconductor device] The semiconductor device actually equipped with the semiconductor chip package of the present invention is, for example, provided for use in electrical products (for example, computers, mobile phones, smart phones, tablet-type devices, wearable devices, digital devices, etc.) Various semiconductor devices such as cameras, medical equipment, and televisions, etc.) and vehicles (such as locomotives, automobiles, trains, ships, and 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, "parts" and "%" of "amount" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Manufacture of samples for peel strength measurement> (1) Primer treatment of inner layer circuit board A double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm) of glass cloth base epoxy resin on which inner layer circuits are formed , R5715ES manufactured by PANASONIC) were dipped in CZ8100 manufactured by Merck to roughen the copper surface.

(2) Lamination of resin sheets The resin sheets prepared in Examples and Comparative Examples were used a batch-type vacuum pressure laminator (Nikko Metal Co., Ltd. two-process stacking laminator "CVP700") to make the resin The method of connecting the composition layer to the inner circuit substrate is laminated on both sides of the inner circuit substrate. The lamination method is carried out in the form of pressing for 30 seconds at 100° C. and a pressure of 0.74 MPa after decompressing for 30 seconds to bring the air pressure below 13 hPa. Next, hot pressing was carried out for 60 seconds at 100° C. and a pressure of 0.5 MPa. The obtained laminated board with the resin composition layer was heat-treated at 180° C. for 30 minutes to harden the resin composition layer to obtain a laminated board with a hardened product.

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

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

<Measurement and Evaluation of the Tensile Peel Strength (Peel Strength) of the Metal Layer> In the evaluation substrate B, the metal layer was cut into a part with a width of 10mm and a length of 100mm, and one end was peeled off, and a jig (AUTOCOM manufactured by DSE Co., Ltd. was used) Type testing machine "AC-50C-SL"), at room temperature, measure the load (kgf/cm) when peeling 20mm in the vertical direction at a speed of 50mm/min, and obtain the peel strength.

<Preparation of cured product for evaluation of elastic modulus> The untreated side of the release PET film ("501010" manufactured by Linde Co., Ltd., thickness 38 μm, 240 mm square) is connected to a glass cloth base epoxy resin double-sided copper-clad laminate (Panasonic "R5715ES" made by Denko Corporation, thickness 0.7mm, 255mm square) is installed on the double-sided copper-clad laminate of glass cloth base epoxy resin, and the four sides of the release PET film are made of polyimide adhesive tape (width 10mm) fixed.

Each resin sheet (167×107 mm square) prepared in the examples and comparative examples was formed into a release PET The release surface of the film is connected to the resin composition layer, and the center is laminated. The lamination process was carried out by depressurizing the pressure for 30 seconds so that the air pressure became 13 hPa or less, and then performing crimping at 100° C. and a pressure of 0.74 MPa for 30 seconds.

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

After thermal curing, the polyimide adhesive tape is peeled off, and the resin composition layer is separated from the double-sided copper-clad laminate of glass cloth base material epoxy resin. Then, the release PET film was peeled off from the resin composition layer to obtain a thin sheet-shaped cured product (cured product for evaluation).

<Measurement of modulus of elasticity> The hardened product for evaluation was cut out into the shape of dumbbell No. 1 to prepare a test piece. The tensile strength of the test piece was measured using a tensile testing machine "RTC-1250A" manufactured by Orientec Corporation, and the modulus of elasticity at 23° C. was obtained. The measurement method was implemented based on JIS K7127. This operation was repeated 3 times, and the average values obtained are shown in the table.

<Evaluation of Warpage> The resin sheets obtained in Examples and Comparative Examples were laminated on glass using a batch-type vacuum pressure laminator (Nikko Metal Co., Ltd. 2-process stacking laminator "CVP700"). Copper-clad laminate on both sides of cloth substrate BT resin (copper foil thickness 18μm, substrate thickness 0.15mm, "HL832NSF LCA" manufactured by Mitsubishi Gas Chemical Co., Ltd., size 15cm×18cm) on one side, after peeling off the PET release liner, at 100 ℃, 30 minutes, and then under the conditions of 180 ℃, 30 minutes, after thermal hardening, place it on a flat surface to confirm its warpage. The average value of the warpage of each of the four corners is less than 1 cm, marked as "○", 1 to 2 cm is marked as "△", and 2 cm or more is marked as "×".

＜Measurement of thermal conductivity of cured product＞

(1) Manufacture of hardened samples

The resin coatings prepared in Examples and Comparative Examples were coated with an alkyd resin release agent (manufactured by Linde Co., Ltd. "AL-5") is applied to a release-treated PET film ("LUMMIOR R80" manufactured by Toray Co., Ltd., thickness 38 μm, softening point 130°C), and then dried at 80°C~100°C (average 90°C) After 7 minutes, a resin composition layer was obtained.

Using a batch-type vacuum pressure laminator (second-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 the curing conditions, the resin composition layer was cured to obtain a cured product sample. In the lamination method, the pressure was reduced to 13 hPa or less over 30 seconds, followed by pressing at 100° C. and a pressure of 0.4 MPa for 20 seconds.

(2) Determination of thermal diffusivity α

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

(3) Determination of specific heat capacity Cp

Using a differential scanning calorimeter ("DSC7020" manufactured by SII Nanotechnology Co., Ltd.), the hardened sample was heated from -40°C at 10°C/min to 80°C. Based on the measurement results, the temperature of the hardened sample was calculated. Specific heat capacity Cp (J/kg.K) at 25°C.

(4) Determination of density ρ

The density (kg/m ³ ) of the hardened sample was measured using an analytical balance XP105 (using a specific gravity measurement kit) manufactured by Mettler Toled.

(5) Calculation of thermal conductivity λ

Substitute the thermal diffusivity α (m ² /s), specific heat capacity Cp (J/kg.K), and density ρ (kg/m ³ ) obtained in (2) to (4) above into the following formula (I) , 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 obtained in Examples and Comparative Examples was measured. Using UBM company type Rheosol-G3000, resin amount 1g, diameter 18mm parallel plate, from the initial temperature of 60 ℃ to 200 ℃, the measurement is carried out at a heating rate of 5 ℃/min, a measurement temperature interval of 2.5 ℃, and a vibration of 1 Hz/deg. conditions to measure the melt viscosity.

<Synthesis Example 1: Synthesis of Polymer Compound 1>

In a reaction container, 69 g of G-3000 (difunctional hydroxyl-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g/eq., solid content 100% by mass: manufactured by Nippon Soda Co., Ltd.) , 40 g of IPUZOURU 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin dilauryl were uniformly mixed and dissolved. After reaching a uniform state, the temperature was raised to 50° C., and 8 g of isophorone diisocyanate (manufactured by Evonik Degussa Japan, IPDI, isocyanate group equivalent = 113 g/eq.) was added while stirring, and the reaction was carried out for about 3 hours. Next, the reactant was cooled to room temperature, and 23 g of cresol-novolak resin (KA-1160, manufactured by DIC Corporation, hydroxyl equivalent=117g/eq.) was mixed with ethyl diethylene glycol acetate (made by DAICEL Corporation). ) 60g was added therein, 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 disappears. When the NCO peak disappears, it is regarded as the end of the reaction. After the reactant is cooled to room temperature, it is filtered through a filter cloth with a mesh size of 100 μm to obtain a polymer compound 1 (non-volatile) with a polybutadiene structure and phenolic hydroxyl group Ingredient 50% by mass).

<Synthesis Example 2: Synthesis of Polymer Compound 2>

In a reaction container, 80 g of polycarbonate diol (number average molecular weight: about 1,000, hydroxyl equivalent: 500, non-volatile content: 100%, "C-1015N" manufactured by KURARAY Co., Ltd.) and 0.01 g of dibutyltin dilauryl It was uniformly dissolved in 37.6 g of diethylene glycol monoethyl ether acetate ("ethyl diethylene glycol acetate" manufactured by DAICEL). Next, this mixture was heated up to 50 degreeC, and 27.8 g of toluene-2, 4- diisocyanates (isocyanate group equivalent weight: 87.08) were added with stirring, and reaction was performed for about 3 hours. Next, this reactant is cooled to room temperature, and 14.3 g of benzophenone tetracarboxylic dianhydride (acid anhydride equivalent: 161.1), 0.12 g of triethylenediamine, and diethylene glycol monoethyl ether acetate (manufactured by DAICEL Co., Ltd.) "Ethyl diethylene glycol acetate") 84.0g was added there, and it heated up to 130 degreeC while stirring, and performed reaction for about 4 hours. Use FT-IR to confirm whether the NCO peak at 2250cm ^-1 disappears. When the NCO peak disappears, it is regarded as the end of the reaction. After the reactant is cooled to room temperature, it is filtered through a filter cloth with a mesh size 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>

Into a 20ml vial, add 0.01g of thermally conductive filler, 0.2g of nonionic dispersant (manufactured by NOF Corporation "T208.5"), 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 analyzer ("SALD2200" manufactured by Shimadzu Corporation), and irradiated with ultrasonic waves for 10 minutes in a cycle. Afterwards, the ultrasonic wave was stopped, and the particle size distribution was measured under the condition that the sample was maintained in circulation, and the average particle size of the thermally conductive filler was obtained. In addition, the refractive index at the time of measurement was set at 1.45-0.001i.

<Measurement of Specific Surface Area of Thermally Conductive Filler>

The specific surface area was determined by the nitrogen BET method using an automatic specific surface area measuring device ("Macsorb HM-1210" manufactured by MOUNTECH Corporation).

<Thermally conductive filler used>

Alumina 1: A mixture of aluminas having 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 Co., Ltd. "KBM573" (N-phenyl-3-amine Propyltrimethoxysilane) Surface Treater

Alumina 2: A mixture of aluminas having 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 Co., Ltd. "KBM5783" (N-phenyl-3-amine octyltrimethoxysilane) surface treater

Alumina 3: A mixture of aluminas 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 Co., Ltd. "KBM403" (3-glycidoxypropoxypropyl Trimethoxysilane) Surface Treater

Alumina 4: A mixture of aluminas 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 Co., Ltd. "KBM903" (3-aminopropyltrimethoxy base silane) surface treater

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

Resin coating 1 was coated with an alkyd resin-based release agent ("AL-5" manufactured by Linde Co., Ltd.) using a slit coater so that the thickness of the dried resin composition layer was 50 μm. On the PET film ("LUMMIOR R80" manufactured by Toray Corporation, thickness 38μm, softening point 130°C, also known as "release PET"), dry at 80°C to 100°C (average 90°C) for 5 minutes , and the resin sheet 1 was obtained.

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

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

<Example 4> Six parts of aminophenol-type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g/eq), liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Bisphenol A type epoxy resin and bisphenol F type epoxy resin 1:1 mixture (mass ratio), epoxy equivalent: 169g/eq) 5 parts, bixylenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation " YX4000H", 2 parts of epoxy equivalent: 185g/eq), 2 parts of biphenyl type epoxy resin (Nippon Kayaku "NC3100", epoxy equivalent: 258g/eq), 2 parts, dissolved in 10 parts of methyl ethyl ketone , and then mixed 270 parts of alumina 2, 24 parts of polymer compound 1 (solid content 50% by mass, number average molecular weight 5500), active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation, active ester equivalent 223g/eq , toluene solution with 65% solid content) 3 parts, solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 215g/eq, used in the form of methyl ethyl ketone solution with 50% solid content ) 2 parts, hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with a solid content of 10% by mass) 1 part, 15 parts of methyl ethyl ketone, uniformly dispersed using a high-speed rotary mixer , and made the resin coating 4. Also, in Example 1, except that the resin coating 1 was changed to the resin coating 4, the resin sheet 4 was prepared in the same manner as in Example 1.

<Example 5>

Six parts of aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g/eq), liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A ring 1:1 mixture (mass ratio) of epoxy resin and bisphenol F-type epoxy resin, epoxy equivalent: 169g/eq) 5 parts, bixylenol-type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, epoxy Equivalent: 185g/eq), 2 parts of biphenyl type epoxy resin ("NC3100" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 258g/eq), 2 parts, dissolved in 10 parts of methyl ethyl ketone, and then mixed with alumina 1 270 parts, polymer compound 2 (solid content 50% by mass, number average molecular weight 6000) 24 parts, active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation, active ester equivalent 223g/eq, solid content 65% toluene solution) 3 parts, solid naphthol-based hardener ("SN485" manufactured by Nippon Steel Sumikin Chemical Co., Ltd., hydroxyl equivalent 215g/eq, used in the form of a 50% solid content methyl ethyl ketone solution) 2 parts, hardened 1 part of accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with 10 mass % solid content) and 15 parts of methyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to obtain a resin Paint 5. Also, in Example 1, except that the resin coating 1 was changed to the resin coating 5, the resin sheet 5 was prepared in the same manner as in Example 1.

<Comparative example 1>

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

<Comparative example 2>

Six parts of aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g/eq), liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A ring 1:1 mixture (mass ratio) of epoxy resin and bisphenol F-type epoxy resin, epoxy equivalent: 169g/eq) 5 parts, bixylenol-type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical Corporation, epoxy Equivalent: 185g/eq), 2 parts of biphenyl type epoxy resin ("NC3100" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 258g/eq), 2 parts, dissolved in 10 parts of methyl ethyl ketone, and then mixed with alumina 1 270 parts, 26 parts of polymer compound 1 (solid content 50% by mass, number average molecular weight 5500), solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 215g/eq, in solid form 50% methyl ethyl ketone solution) 2 parts, hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), solid content 10 mass % MEK solution) 1 part, methyl 15 parts of acetone were uniformly dispersed using a high-speed rotary mixer to obtain resin coating 7. Also, in Example 1, the resin sheet 7 was prepared in the same manner as in Example 1 except that the resin coating 1 was changed to the resin coating 7 .

<Comparative Example 3> 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 & Sumikin Chemical Co., Ltd., Bisphenol A type epoxy resin and bisphenol F type epoxy resin 1:1 mixture (mass ratio), epoxy equivalent: 169g/eq) 5 parts, bixylenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation " YX4000H", 2 parts of epoxy equivalent: 185g/eq), 2 parts of biphenyl type epoxy resin (Nippon Kayaku "NC3100", epoxy equivalent: 258g/eq), 2 parts, dissolved in 10 parts of methyl ethyl ketone , and then mixed 270 parts of alumina 3, 24 parts of polymer compound 1 (solid content 50% by mass, number average molecular weight 5500), solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 215g /eq, used in the form of 50% solid content of methyl ethyl ketone solution) 6 parts, hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), solid content of 10 mass% MEK solution) 1 part and 15 parts of methyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to prepare resin coating 8. Also, in Example 1, except that the resin coating 1 was changed to the resin coating 8, the resin sheet 8 was prepared in the same manner as in Example 1.

<Comparative Example 4> 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 & Sumikin Chemical Co., Ltd., Bisphenol A type epoxy resin and bisphenol F type epoxy resin 1:1 mixture (mass ratio), epoxy equivalent: 169g/eq) 5 parts, bixylenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation " YX4000H", 2 parts of epoxy equivalent: 185g/eq), 2 parts of biphenyl type epoxy resin (Nippon Kayaku "NC3100", epoxy equivalent: 258g/eq), 2 parts, dissolved in 10 parts of methyl ethyl ketone , and then mixed 270 parts of alumina 4, 24 parts of polymer compound 1 (solid content 50% by mass, number average molecular weight 5500), solid naphthol-based hardener ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 215g /eq, used in the form of 50% solid content of methyl ethyl ketone solution) 6 parts, hardening accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), solid content of 10 mass% MEK solution) 1 part and 15 parts of methyl ethyl ketone were uniformly dispersed using a high-speed rotary mixer to prepare resin coating 9. Also, in Example 1, except that the resin coating 1 was changed to the resin coating 9, the resin sheet 9 was obtained in the same manner as in Example 1.

The descriptions in the following tables, etc., are as follows. Content of component (A): When the non-volatile content of the resin component after removing component (C) is 100 mass % Content of component (C): When the non-volatile content of the resin composition is 100 mass % Content

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

100‧‧‧semiconductor chip package 110‧‧‧semiconductor chip 120‧‧‧sealing layer 130‧‧‧rewiring forming layer (insulating layer) 140‧‧‧conducting layer (rewiring layer) 150‧‧‧solder resist layer 160‧‧‧bumps

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

Claims (17)

A resin composition, characterized by containing: (A) polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkylene oxide structure, poly Polymer compound with at least one structure selected from isoprene structure, polyisobutylene structure, and polycarbonate structure, (B) epoxy resin, (C) thermally conductive filler, and (D) active ester hardener , wherein, (A) component coefficient average molecular weight (Mn) is 1,000~1,000,000, or one or more selected from resins with a glass transition temperature of 25°C or less, and resins that are liquid at 25°C, (C ) component content is 85% by mass or more when the non-volatile content in the resin composition is 100% by mass. The resin composition as claimed in item 1, wherein, the peel strength of the hardened product formed by thermal curing 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 above. The resin composition according to claim 1, wherein the component (C) contains alumina. The resin composition according to claim 1, wherein component (C) is surface-treated with an aminosilane-based coupling agent. The resin composition as in claim 1, wherein component (C) is surface-treated with N-phenyl-3-aminoalkyltrimethoxysilane. The resin composition as claimed in 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. Above K, 5.0W/m. Below K. The resin composition according to claim 1, wherein component (A) has a functional group capable of reacting with component (B). The resin composition according to claim 1, wherein the component (A) has at least one functional group selected from hydroxyl group, acid anhydride group, phenolic hydroxyl group, epoxy group, isocyanate group and urethane group. The resin composition according to claim 1, wherein component (A) has an imide structure. The resin composition according to claim 1, wherein component (A) has a phenolic hydroxyl group. The resin composition according to claim 1, wherein component (A) has a polybutadiene structure and has a phenolic hydroxyl group. The resin composition according to claim 1, which is a resin composition for an insulating layer of a semiconductor chip package. The resin composition according to claim 1, which is a resin composition for an insulating layer of a circuit substrate formed by a semi-additive process (Semi-Additive Process). A resin sheet, characterized by comprising: a support body, and a resin composition layer comprising the resin composition according to any one of claims 1 to 13 disposed on the support body. A circuit board characterized by comprising: an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 13. A semiconductor chip package, characterized by comprising: the circuit substrate of claim 15, 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 13, or a semiconductor chip sealed by the resin sheet of claim 14.

Images