JP6787210B2 - Resin composition - Google Patents

Description

The present invention relates to resin compositions. Furthermore, the present invention relates to a resin sheet, a circuit board, and a semiconductor chip package using a resin composition.

In recent years, electronic devices have become smaller and more sophisticated, and the mounting density of semiconductor elements on printed wiring boards tends to increase. Along with the high functionality of the mounted semiconductor elements, there is a demand for a technology for efficiently diffusing the heat generated by the semiconductor elements. When the resin composition containing the thermally conductive filler is cured to form the insulating layer, the thermal conductivity of the obtained insulating layer can be improved by increasing the content of the thermally conductive filler in the resin composition. However, if the content of the thermally conductive filler is increased to such an extent that sufficient thermal conductivity is exhibited, the obtained insulating layer tends to be inferior in adhesion strength to the metal layer for forming the wiring.

For example, in Patent Document 1, by using an insulating layer obtained by curing a resin composition containing aluminum nitride or silicon nitride for a printed wiring board, thermal diffusibility is exhibited and the surface roughness is low, and the conductor layer is used. It is disclosed that the adhesion strength (peel strength) diffuses heat with good adhesion.

International Publication No. 2014/208352

In recent years, electronic devices have become smaller and more sophisticated, and substrates have become thinner and coreless. In addition to thermal diffusivity and adhesion strength (peeling strength), when forming an insulating layer, the material has become more compact and highly functional. It has become necessary to suppress the warpage that occurs. These performances were in a trade-off relationship, and it was very difficult to design a well-balanced resin.

The present invention has been made to solve the above problems, and provides a cured product having excellent thermal conductivity and peel strength against a metal layer and having a good balance in suppressing the amount of warpage generated when forming an insulating layer. A resin composition that can be obtained; an object of the present invention is to provide a resin sheet, a circuit board, and a semiconductor chip package using the resin composition.

The present inventors are selected from (A) a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisobutylene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. By containing a polymer compound having one or more types of structures, (B) epoxy resin, (C) thermally conductive filler, and (D) active ester curing agent, thermal conductivity and metal layer (particularly plating) are contained. It has been found that an insulating layer having excellent peel strength with respect to the metal layer formed by (the metal layer formed by the above) and excellent in suppressing warpage generated when forming the insulating layer can be obtained, and the present invention has been completed.

That is, the present invention includes the following contents.
[1] (A) One selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. Polymer compounds with the above structure,
(B) Epoxy resin,
A resin composition containing (C) a thermally conductive filler and (D) an active ester curing agent.
[2] The peel strength of the cured product obtained by thermally curing the resin composition at 180 ° C. for 30 minutes and further at 180 ° C. for 60 minutes and the metal layer formed by plating is 0.4 kgf / cm or more [1]. ] The resin composition according to.
[3] The resin composition according to [1] or [2], wherein the content of the component (C) is 85% by mass or more when the non-volatile component in the resin composition is 100% by mass.
[4] The resin composition according to any one of [1] to [3], wherein the component (C) contains alumina.
[5] The resin composition according to any one of [1] to [4], wherein the component (C) is surface-treated with an aminosilane-based coupling agent.
[6] The resin composition according to any one of [1] to [5], wherein the component (C) is surface-treated with N-phenyl-3-aminoalkyltrimethoxysilane.
[7] 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 · K or more and 5.0 W / m · K or less [1] to [6]. The resin composition according to any one of.
[8] The composition according to any one of [1] to [7], wherein the component (A) is at least one selected from a resin having a glass transition temperature of 25 ° C. or lower and a resin liquid at 25 ° C. Resin composition.
[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] Of [1] to [9], the component (A) has one or more functional groups selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. The resin composition according to any one.
[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 a phenolic hydroxyl group.
[14] The resin composition according to any one of [1] to [13], which is a resin composition for an insulating layer of a semiconductor chip package.
[15] The resin composition according to any one of [1] to [14], which is a resin composition for an insulating layer of a circuit board in which a circuit is formed by a semi-additive process method.
[16] A resin sheet having a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [15].
[17] A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [15].
[18] A semiconductor chip package including the circuit board according to [17] and a semiconductor chip mounted on the circuit board.
[19] A semiconductor chip package containing the resin composition according to any one of [1] to [15] or a semiconductor chip sealed with the resin sheet according to [16].

According to the present invention, it is possible to obtain a cured product having excellent thermal conductivity, adhesion strength to a metal layer, particularly a metal layer formed by plating, and a well-balanced suppression of the amount of warpage generated when forming an insulating layer. A resin composition that can be used; a resin sheet, a circuit board, and a semiconductor chip package using the resin composition can be provided.

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

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

[Resin composition]
The resin composition of the present invention has (A) a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisobutylene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. It contains a polymer compound having one or more selected structures, (B) epoxy resin, (C) thermally conductive filler, and (D) active ester curing agent.

By incorporating the component (A), the component (B), the component (C), and the component (D) into the resin composition, an insulating layer excellent in thermal conductivity, peel strength with respect to the metal layer, and suppression of the amount of warpage can be obtained. It becomes possible to obtain. In addition, the above-mentioned resin composition can usually have a low melt viscosity. The resin composition further contains (E) a curing agent, (F) a curing accelerator, (G) an inorganic filler (excluding those corresponding to the component (C)) and (H) a flame retardant, if necessary. obtain. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) One or more selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. Polymer compound with structure>
The resin composition is selected from (A) a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. Contains a polymer compound having one or more types of structures. By incorporating a polymer compound having such a structure into the resin composition, warpage of the cured product can be suppressed. In addition, "(meth) acrylate" refers to methacrylate and acrylate.

More specifically, the component (A) is a polybutadiene structure of polybutadiene, hydrogenated polybutadiene, etc., a polysiloxane structure of silicone rubber, etc., a poly (meth) acrylate structure, a polyalkylene structure (with 2 to 15 carbon atoms). A polyalkylene structure is preferable, a polyalkylene structure having 3 to 10 carbon atoms is more preferable, a polyalkylene structure having 5 to 6 carbon atoms is more preferable), and a polyalkyleneoxy structure (polyalkyleneoxy having 2 to 15 carbon atoms). The structure is preferable, a polyalkyleneoxy structure having 3 to 10 carbon atoms is more preferable, and a polyalkyleneoxy structure having 5 to 6 carbon atoms is more preferable), a polyisobutylene structure, a polyisobutylene structure, and a polycarbonate structure are selected. It is preferable to have one or more types of structures, and one or more types selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyisobutylene structure, a polyisobutylene structure, and a polycarbonate structure. It preferably has a structure, and more preferably has one or more structures selected from a polybutadiene structure, a polyisobutylene structure, and a polycarbonate structure.

The component (A) preferably has a high molecular weight in order to exhibit flexibility, and the number average molecular weight (Mn) is preferably 1,000 to 1,000,000, more preferably 5,000 to 9,000. It is 000. The number average molecular weight (Mn) is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

The component (A) is preferably one or more resins selected from a resin having a glass transition temperature (Tg) of 25 ° C. or lower and a resin liquid at 25 ° C. in order to exhibit flexibility.

The glass transition temperature of the resin having a glass transition temperature (Tg) of 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 can usually be −15 ° C. or higher. The resin that is liquid at 25 ° C. is preferably a resin that is liquid at 20 ° C. or lower, and more preferably a resin that is liquid at 15 ° C. or lower.

The component (A) preferably has a functional group capable of reacting with the component (B) from the viewpoint of improving the mechanical strength of the cured product. The functional groups that can react with the component (B) include functional groups that appear by heating.

In one preferred embodiment, the functional group capable of reacting with the component (B) is selected from the group consisting of a hydroxy group, a carboxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. It is a functional group that is more than a species. Among them, as the functional group, a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group are preferable, a hydroxy group, an acid anhydride group, a phenolic hydroxyl group and an epoxy group are more preferable, and phenol. A sex hydroxyl group is particularly preferable.

A preferred embodiment of the component (A) is a butadiene resin. The butadiene resin is preferably a butadiene resin that is liquid at 25 ° C. or has a glass transition temperature of 25 ° C. or lower, and is preferably a hydride polybutadiene skeleton-containing resin, a hydroxy group-containing butadiene resin, a phenolic hydroxyl group-containing butadiene resin, a carboxy group-containing butadiene resin, and acid anhydride. One or more resins selected from the group consisting of a material group-containing butadiene resin, an epoxy group-containing butadiene resin, an isocyanate group-containing butadiene resin, and a urethane group-containing butadiene resin are more preferable, and a phenolic hydroxyl group-containing butadiene resin is further preferable. Examples of the hydrogenated polybutadiene skeleton-containing resin include a hydrogenated polybutadiene skeleton-containing epoxy resin. Examples of the phenolic hydroxyl group-containing butadiene resin include resins having a polybutadiene structure and having a phenolic hydroxyl group.

Here, the "butadiene resin" refers to a resin containing a polybutadiene structure, and in these resins, the polybutadiene structure may be contained in the main chain or the side chain. The butadiene structure may be partially or wholly hydrogenated. Here, the "hydrogenated polybutadiene skeleton-containing resin" means a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and the polybutadiene skeleton does not necessarily have to be a completely hydrogenated resin.

The number average molecular weight (Mn) of the butadiene resin is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, more preferably 7,500 to 30,000, still more preferably 10,000 to 10,000. It is 15,000. Here, the number average molecular weight (Mn) of the resin is a polystyrene-equivalent number average molecular weight measured by using GPC (gel permeation chromatography).

When the butadiene resin has a functional group, the functional group equivalent is preferably 100 to 10000, more preferably 200 to 5000. The functional group equivalent is the number of grams of the resin containing 1 gram equivalent of the functional group. For example, the epoxy group equivalent can be measured according to JIS K7236. The hydroxyl group equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

Specific examples of the butadiene resin include "Ricon 657" (polybutadiene containing an epoxy group), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", and "Ricon 131MA10" manufactured by Clay Valley. "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing acid anhydride group), "JP-100", "JP-200" (epoxidized polybutadiene), "GQ-1000" (made by Nippon Soda Co., Ltd.) Polybutadiene with hydroxyl groups and carboxyl groups), "G-1000", "G-2000", "G-3000" (polybutadiene with hydroxyl groups at both ends), "GI-1000", "GI-2000", "GI-3000" ( Hydroxyl-terminated polybutadiene at both ends), "PB3600", "PB4700" (polybutadiene skeleton epoxy compound), "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (styrene, butadiene, and styrene block) manufactured by Daicel. (Epoxy compound of copolymer), “FCA-061L” (hydrogenated polybutadiene skeleton epoxy compound) manufactured by Nagase ChemteX Corporation, “R-45EPT” (polybutadiene skeleton epoxy compound), and the like.

Further, as another preferable embodiment of the component (A), a resin having an imide structure can also be used. Examples of the resin having an imide structure include linear polyimides made from hydroxyl group-terminated polybutadiene, diisocyanate compounds and tetrabasic acid anhydrides (polyimides described in JP-A-2006-37083 and International Publication No. 2008/153208). Can be mentioned. The content of the polybutadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description of JP-A-2006-37083 and International Publication No. 2008/153208 can be referred to, and the contents thereof are incorporated in the present specification.

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

Moreover, a preferable embodiment of the component (A) is a carbonate resin. As the carbonate resin, a carbonate resin having a glass transition temperature of 25 ° C. or lower is preferable, and a hydroxy group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxy group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an epoxy group-containing carbonate resin, One or more resins selected from the group consisting of an isocyanate group-containing carbonate resin and a urethane group-containing carbonate resin are preferable. Here, the "carbonate resin" refers to a resin containing a polycarbonate structure, and in these resins, the polycarbonate structure may be contained in the main chain or the side chain.

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

Specific examples of the carbonate resin include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090" and "C-3090" (polycarbonate diol) manufactured by Kuraray. And so on.

Further, a linear polyimide made from a hydroxyl group-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride can also be used. The content of the polycarbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. The details of the polyimide resin can be referred to in International Publication No. 2016/129541, which is incorporated herein by reference.

Another preferred embodiment of the component (A) is an acrylic resin. As the acrylic resin, an acrylic resin having a glass transition temperature (Tg) of 25 ° C. or lower is preferable, and a hydroxy group-containing acrylic resin, a phenolic hydroxyl group-containing acrylic resin, a carboxy group-containing acrylic resin, an acid anhydride group-containing acrylic resin, and an epoxy group One or more resins selected from the group consisting of a containing acrylic resin, an isocyanate group-containing acrylic resin, and a urethane group-containing acrylic resin are more preferable. Here, the "acrylic resin" refers to a resin containing a poly (meth) acrylate structure, and in these resins, the poly (meth) acrylate structure may be contained in the main chain or the side chain. Good.

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

When the acrylic resin has a functional group, the functional group equivalent is preferably 1000 to 50000, more preferably 2500 to 30000.

Specific examples of the acrylic resin include Teisan resins "SG-70L", "SG-708-6", "WS-023", "SG-700AS", and "SG-280TEA" (carboxy group) manufactured by Nagase ChemteX Corporation. Containing acrylic acid ester copolymer resin, acid value 5-34 mgKOH / g, weight average molecular weight 400,000-900,000, Tg-30-5 ° C), "SG-80H", "SG-80H-3", "SG" -P3 "(epoxy group-containing acrylic ester copolymer resin, epoxy equivalent 4761 to 14285 g / eq, weight average molecular weight 350,000 to 850,000, Tg 11 to 12 ° C.)," SG-600TEA "," SG-790 "" (Hydroxy group-containing acrylic ester copolymer resin, hydroxyl value 20-40 mgKOH / g, weight average molecular weight 500,000-1.2 million, Tg-37-32 ° C), "ME-2000" manufactured by Negami Kogyo Co., Ltd., " "W-116.3" (carboxy group-containing acrylic acid ester copolymer resin), "W-197C" (hydroxyl group-containing acrylic acid ester copolymer resin), "KG-25", "KG-3000" (epoxy group) (Containing acrylic acid ester copolymer resin) and the like.

Further, a preferred embodiment of the component (A) is a siloxane resin, an alkylene resin, an alkyleneoxy resin, and an isobutylene resin.

Specific examples of the siloxane resin include "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shinetsu Silicone Co., Ltd., amine group-terminated polysiloxane, and linear polyimide made from tetrabasic acid anhydride (international). Publication No. 2010/053185) and the like. Here, the "siloxane resin" refers to a resin containing a polysiloxane structure, and in these resins, the polysiloxane structure may be contained in the main chain or the side chain.

Specific examples of the alkylene resin and the alkyleneoxy resin are "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Co., Ltd. and "YX-7180" manufactured by Mitsubishi Chemical Corporation (resin containing an alkylene structure having an ether bond). And so on. "EXA-4850-150" "EXA-4816" "EXA-4822" manufactured by DIC Corporation "EP-4000", "EP-4003", "EP-4010", and "EP-4011" manufactured by ADEKA, new Examples thereof include "BEO-60E" and "BPO-20E" manufactured by New Japan Chemical Co., Ltd. and "YL7175" and "YL7410" manufactured by Mitsubishi Chemical Corporation. Here, the "alkylene resin" refers to a resin containing a polyalkylene oxy structure, and the "alkylene oxy resin" refers to a resin containing a polyalkylene oxy structure. In these resins, the polyalkylene structure and the polyalkylene oxy structure may be contained in the main chain or the side chain.

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

Further, preferred embodiments of the component (A) include acrylic rubber particles, polyamide fine particles, silicone particles and the like. Specific examples of the acrylic rubber particles include fine particles of a resin that is insoluble and insoluble in an organic solvent by chemically cross-linking a resin exhibiting rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber. Specifically, XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyroid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (manufactured by Ganz Kasei Co., Ltd.), Pararoid EXL2655, EXL2602 (manufactured by Kureha Chemical Industry Co., Ltd.) ) Etc. can be mentioned. Specific examples of the polyamide fine particles may be any aliphatic polyamide such as nylon, and any flexible skeleton such as polyamide-imide. Specifically, VESTOSINT 2070 (manufactured by Daiselhurus) or , SP500 (manufactured by Toray Industries, Inc.) and the like.

The content of the component (A) in the resin composition is when the non-volatile component (resin component) of the resin composition excluding the component (C) and the component (G) is 100% by mass from the viewpoint of imparting flexibility. It is preferably 65% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, and even more preferably 50% by mass or less. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and even more preferably 25% by mass or more.

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

Examples of the epoxy resin include bixilenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type epoxy resin. Naftor novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin having aromatic structure, aromatic structure Glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, epoxy resin having a butadiene structure having an aromatic structure, alicyclic having an aromatic structure Formula epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, naphthylene ether type epoxy resin, trimethylol type epoxy resin having an aromatic structure , Tetraphenyl ethane type epoxy resin, aminophenol type epoxy resin and the like. One type of epoxy resin may be used alone, or two or more types may be used in combination. The component (B) is preferably one or more selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, aminophenol type epoxy resin and naphthalene type epoxy resin.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, one molecule has two or more epoxy groups, and a liquid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”) and one molecule have three or more epoxy groups. It is preferable to contain a solid epoxy resin (hereinafter referred to as "solid epoxy resin") at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, a resin composition having excellent flexibility can be obtained. In addition, the breaking strength of the cured product of the resin composition is also improved.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin having an aromatic structure, and glycidylamine type epoxy resin having an aromatic structure. , Phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, aminophenol type epoxy resin and epoxy having a butadiene structure having an aromatic structure. Resins are preferable, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, aminophenol type epoxy resin and naphthalene type epoxy resin are more preferable, bisphenol A type epoxy resin, bisphenol F type epoxy resin, aminophenol. Molded epoxy resins are even more preferred. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, and "828US" and "jER828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. , "JER806", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Corporation. (A mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, and "Ceroxide 2021P" (having an ester skeleton) manufactured by Daicel Co., Ltd. (Ali-ring type epoxy resin), “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd., and “YX7400” (high resilience epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthylene ether type epoxy resin. Anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin. Is more preferable, and a naphthalene type tetrafunctional epoxy resin and a naphthylene ether type epoxy resin are further preferable. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC. Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", "HP-7200HHH" ( Dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN" manufactured by Nippon Kayakusha -502H "(Trisphenol type epoxy resin)," NC7000L "(Naftor novolac type epoxy resin)," NC3000H "," NC3000 "," NC3000L "," NC3100 "(biphenyl type epoxy resin), manufactured by Nippon Steel & Sumitomo Metal Corporation "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixilenol type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. , "YL7760" (bisphenol AF type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" (fluoren) manufactured by Mitsubishi Chemical Co., Ltd. Type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "jER1031S" (tetraphenylethane type epoxy resin), "157S70" (bisphenol novolac type epoxy resin), manufactured by Mitsubishi Chemical Co., Ltd. "YX4000HK" (Bixilenoll type epoxy resin), "YX8800" (Anthracen type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" manufactured by Mitsubishi Chemical Co., Ltd. (Fluoren) Type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (B), their quantity ratio (solid epoxy resin: liquid epoxy resin) is 1: 0.1 to 1:15 in terms of mass ratio. The range is preferred. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within such a range, i) appropriate adhesiveness is provided when used in the form of a resin sheet, and ii) when used in the form of a resin sheet. Sufficient flexibility can be obtained, handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin: liquid epoxy resin) is in the range of 1: 0.3 to 1:10 in terms of mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 8 is even more preferable.

The content of the epoxy resin in the resin composition is preferably 1% by mass or more when the non-volatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. It is more preferably 2% by mass or more, still more preferably 3% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 6% by mass or less.

Further, the content of the epoxy resin in the resin composition is a non-volatile component of the resin composition excluding the component (C) and the component (G) from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. When it is 100% by mass, it is 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 55% by mass or less.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

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

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

The material of the component (C) is not particularly limited as long as the thermal conductivity is within the above range. Examples of the material contained in the component (C) include alumina, aluminum nitride, boron nitride, silicon carbide and the like. Of these, alumina is particularly suitable. The component (C) may be used alone or in combination of two or more. Further, two or more kinds of the same materials may be used in combination.

The average particle size of the component (C) is preferably 5 μm or less, more preferably 4 μm or less, still more preferably 3 μm or less, from the viewpoint of obtaining an insulating layer having excellent both thermal conductivity and peel strength and improving the filling property. It is preferably 0.1 μm or more, more preferably 1.0 μm or more, and further preferably 1.5 μm or more. The average particle size of the component (C) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, one in which the component (C) is dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd., "SALD2200" manufactured by Shimadzu Corporation, or the like can be used. Specifically, it can be measured according to the method described in <Measurement of average particle size of thermally conductive filler> described later.

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

The component (C) is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilazane compound, from the viewpoint of enhancing moisture resistance and dispersibility. It may be treated with one or more surface treatment agents such as a titanate-based coupling agent. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Kagaku Kogyo Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM5783" (N-) manufactured by Shin-Etsu Chemical Co., Ltd. Phenyl-3-aminooctyltrimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM" manufactured by Shin-Etsu Chemical Co., Ltd. -4803 ”(long-chain epoxy type silane coupling agent) and the like. Among them, from the viewpoint of lowering the melt viscosity and improving the laminate property, the component (C) is preferably surface-treated with an aminosilane-based coupling agent, and N-phenyl-3-aminopropyltrimethoxysilane, It is preferable that the surface is treated with N-phenyl-3-aminoalkyltrimethoxysilane such as N-phenyl-3-aminooctyltrimethoxysilane, and the surface is treated with N-phenyl-3-aminooctyltrimethoxysilane. It is more preferable that it is.

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

<(D) Active ester curing agent>
The resin composition of the present invention contains (D) an active ester curing agent. The active ester curing agent is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenol, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.

As the active ester compound, the active ester compound disclosed in JP-A-2004-277460 and JP-A-2013-40270 may be used, or a commercially available active ester compound may be used. Commercially available products of the active ester curing agent include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-65TM" as active ester compounds containing a dicyclopentadiene type diphenol structure. , "EXB-8000L-65TM" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, and "DC808" (Mitsubishi) as an active ester compound containing an acetylated product of phenol novolac. Chemical Co., Ltd.), "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester curing agent which is an acetylated product of phenol novolac "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.), and "EXB9050L-62M" manufactured by DIC Co., Ltd. as active ester curing agents which are benzoylated products of Phosphorus atom-containing active ester compound) and the like.

The content of the component (D) is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, when the non-volatile component in the resin composition is 100% by mass. The lower limit is not particularly limited, but is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. By keeping the content of the component (D) within such a range, the thermal conductivity and the peel strength can be improved.

<(E) Hardener>
The resin composition of the present invention may contain (E) a curing agent in addition to the component (D). However, the component (E) referred to here does not include the active ester curing agent (D). The curing agent (E) is not particularly limited as long as it has a function of curing the resin such as the component (B), and is, for example, a phenol-based curing agent, a naphthol-based curing agent, a benzoxazine-based curing agent, and a cyanate ester-based curing agent. , And a carbodiimide-based curing agent. The curing agent may be used alone or in combination of two or more. The component (D) is preferably one or more selected from a phenol-based curing agent, a naphthol-based curing agent, and a cyanate ester-based curing agent, and preferably one or more selected from the phenol-based curing agent. preferable.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the wiring layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the wiring layer.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" and "CBN" manufactured by Nippon Kayaku Co., Ltd. , "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" manufactured by Nippon Steel & Sumitomo Metal Corporation, "TD-" manufactured by DIC Corporation. 2090 ”,“ LA-7052 ”,“ LA-70 ”
54 ”,“ LA-1356 ”,“ LA-3018-50P ”,“ EXB-9500 ”,“ HPC-9500 ”,“ KA-1160 ”,“ KA-1163 ”,“ KA-1165 ”, Gun Ei Chemical Industry Examples thereof include "GDP-6115L" and "GDP-6115H" manufactured by the same company.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., "Pd" and "FA" manufactured by Shikoku Chemicals Corporation.

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidene diphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (part of bisphenol A disicanate) manufactured by Ronza Japan. Alternatively, a prepolymer in which all of them are triazined to form a trimer) and the like can be mentioned.

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

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

<(F) Curing accelerator>
The resin composition of the present invention may contain (F) a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like, and phosphorus-based curing accelerators and amine-based curing accelerators. Curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. Examples thereof include (5,4,0) -undecene, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 1,2-dimethyl imidazole, and the like. 2-Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2-Phenylimidazolium trimerite, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4- Diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-Phenylimidazoline and other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadesylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biganide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

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

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

<(G) Inorganic filler (excluding those corresponding to (C) component)>
The resin composition of the present invention may contain (G) an inorganic filler. However, the (G) inorganic filler referred to here does not include the one corresponding to the (C) thermally conductive filler. The material of the component (G) is not particularly limited, but for example, silica, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and hydroxide. Aluminum, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconate oxide, barium titanate , Barium titanate titanate, barium zirconate titanate, calcium zirconate titer, zirconate zirconate, zirconate titnate titanate and the like. Of these, silica is particularly suitable. Further, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

The average particle size of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, still more preferably 2.2 μm or less, from the viewpoint of improving circuit embedding property and obtaining an insulating layer having low surface roughness. It is preferably 2 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, and further preferably 0.1 μm or more. The average particle size of the inorganic filler can be measured in the same manner as the component (C). Commercially available products of inorganic fillers having such an average particle size include, for example, "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatex, and "UFP-30" manufactured by Denki Kagaku Kogyo. , Tokuyama Corporation "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N", Admatex "SC2500SQ", "SO-C6", "SO-C4", "SO-C2" , "SO-C1" and the like.

From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler contains aminosilane-based coupling agent, epoxysilane-based coupling agent, mercaptosilane-based coupling agent, silane-based coupling agent, alkoxysilane compound, organosilazane compound, and titanate. It is preferable that the treatment is performed with one or more surface treatment agents such as a system coupling agent. Specific commercial products of surface treatment agents are as described above.

When the resin composition contains the component (G), the content of the component (G) in the resin composition is not particularly limited, but when the non-volatile component in the resin composition is 100% by mass, it is preferably 0. It is 1% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.

<(H) Flame Retardant>
The resin composition may contain (H) flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. The flame retardant may be used alone or in combination of two or more.

As the flame retardant, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd.

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

<(I) Arbitrary additive>
The resin composition may further contain other additives, if necessary, and such other additives include, for example, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds. In addition, resin additives such as binders, thickeners, defoamers, leveling agents, adhesion-imparting agents, and colorants can be mentioned.

<Physical properties of resin composition>
The cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 30 minutes and further at 180 ° C. for 60 minutes exhibits a characteristic of excellent peel strength with a metal layer, particularly a metal layer formed by plating. That is, it provides an insulating layer having excellent peel strength. For details, when the resin composition of the present invention is heat-treated at 180 ° C. for 30 minutes, a metal layer is formed by plating on the roughened surface of the cured product surface and heat-treated at 180 ° C. for 60 minutes. It exhibits a characteristic of excellent peel strength with a metal layer. The peel strength is preferably 0.4 kgf / cm or more, more preferably 0.45 kgf / cm or more, and further preferably 0.5 kgf / cm or more. On the other hand, the upper limit of the peel strength is not particularly limited, but may be 1.5 kgf / cm or less, 1 kgf / cm or less, or the like. The peel strength can be evaluated according to the method described in <Measurement and evaluation of peel strength (peel strength) of metal layer> described later. The metal layer is preferably a metal layer containing copper, and more preferably a metal layer formed by plating.

The cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 90 minutes exhibits a characteristic of excellent thermal conductivity. That is, it provides an insulating layer having excellent thermal conductivity. The thermal conductivity is preferably 1.5 W / m · K or more, more preferably 1.8 W / m · K or more, and even more preferably 2.0 W / m · K or more. The upper limit of thermal conductivity may be 5.0 W / m · K or less, 4.0 W / m · K or less, or 3.5 W / m · K or less. The thermal conductivity can be evaluated according to the method described in <Measurement of thermal conductivity of cured product> described later.

The cured product obtained by thermosetting the resin composition of the present invention at 180 ° C. for 90 minutes exhibits a characteristic of low elastic modulus at 23 ° C. That is, it provides an insulating layer having a low elastic modulus. The elastic modulus is preferably 25 GPa or less, more preferably 20 GPa or less, still more preferably 15 GPa or less. The lower limit may be 0.1 GPa or more. The elastic modulus can be measured according to the method described in <Measurement of elastic modulus> described later.

The cured product obtained by thermally curing the resin composition of the present invention at 100 ° C. for 30 minutes and further at 180 ° C. for 30 minutes exhibits a characteristic that the amount of warpage is low. That is, it provides an insulating layer with a low amount of warpage. The average value of the amount of warpage of each of the four corners is preferably less than 1 cm. The amount of warpage can be measured according to the method described in <Evaluation of amount of warpage> described later.

The resin composition of the present invention exhibits a characteristic of low melt viscosity. As a result, the laminateability of the resin composition layer of the resin sheet described later is improved, and a cured product of the resin composition having high peel strength can be obtained. The melt viscosity is preferably 500 poise or more, more preferably 1000 poise or more, still more preferably 1500 poise or more, preferably 8500 poise or less, more preferably 8000 poise or less, still more preferably 7500 poise or less, or 7000 poise or less. Is. The melt viscosity can be measured according to the method described in <Measurement of melt viscosity> described later.

The resin composition of the present invention can provide an insulating layer having excellent thermal conductivity and peel strength. Therefore, the resin composition of the present invention forms an insulating layer of a resin composition (resin composition for an insulating layer of a semiconductor chip package) and a circuit board (including a printed wiring board) for forming an insulating layer of a semiconductor chip package. A resin composition (plating) for forming an interlayer insulating layer on which a conductor layer is formed by plating, which can be suitably used as a resin composition (resin composition for an insulating layer of a circuit board). It can be more preferably used as a circuit board on which a conductor layer is formed, that is, a resin composition for an interlayer insulating layer of a circuit board on which a circuit is formed by a semi-additive process method).
It is also suitable as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip) and a resin composition for forming wiring on a semiconductor chip (resin composition for forming a semiconductor chip wiring). Can be used.

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

From the viewpoint of thinning, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, or 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be usually 1 μm or more, 5 μm or more, 10 μm or more, or the like.

Examples of the support include a film made of a plastic material, a metal foil, and a paper pattern, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter abbreviated as "PET") or polyethylene naphthalate (hereinafter abbreviated as "PEN"). ) And other polyesters, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyethers. Examples thereof include ketones and polyethylene. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it.

The surface of the support to be joined to the resin composition layer may be matted or corona-treated.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" and "SK-1" manufactured by Lintec Corporation, which are PET films having a release layer containing an alkyd resin-based release agent as a main component. Examples thereof include "AL-5" and "AL-7", "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Corporation, and "Unipee" manufactured by Unitika.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

For the resin sheet, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, the resin varnish is applied onto a support using a die coater, a compression molding method, or the like, and the resin composition is further dried. It can be manufactured by forming a layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like. Examples thereof include carbitols, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, the resin composition is obtained by drying at 50 ° C. to 150 ° C. for 3 to 10 minutes. A material layer can be formed.

In the resin sheet, a protective film similar to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches. The resin sheet can be rolled up and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

The resin sheet can be suitably used for forming an insulating layer in the manufacture of a semiconductor chip package (insulating resin sheet for a semiconductor chip package). For example, the resin sheet can be suitably used for forming an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board), and an interlayer insulating layer in which a conductor layer is formed by plating is formed on the resin sheet. Therefore, it can be more preferably used (for an interlayer insulating layer of a circuit board that forms a conductor layer by plating). Examples of packages using such a substrate include FC-CSP, MIS-BGA package, and ETS-BGA package.

Further, the resin sheet can be suitably used for encapsulating a semiconductor chip (resin sheet for encapsulating a semiconductor chip) or for forming wiring on a semiconductor chip (resin sheet for forming a semiconductor chip wiring), for example. It can be suitably used for Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), Fan-in type PLP and the like. Further, it can be suitably used as a MUF (Molding Under Filling) material or the like used after connecting a semiconductor chip to a substrate. In addition, the resin sheet can be suitably used for a wide range of other applications that require high insulation reliability, for example, for forming an insulating layer of a circuit board such as a printed wiring board.

Instead of the resin sheet, a prepreg formed by impregnating a sheet-like fiber base material with the resin composition of the present invention may be used.

The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for the prepreg such as glass cloth, aramid non-woven fabric, and liquid crystal polymer non-woven fabric can be used. From the viewpoint of thinning, the thickness of the sheet-shaped fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, still more preferably 600 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited, but may be usually 1 μm or more, 1.5 μm or more, 2 μm or more, or the like.

The prepreg can be produced by a known method such as a hot melt method or a solvent method.

The thickness of the prepreg can be in the same range as the resin composition layer in the resin sheet described above.

[Circuit board]
The circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.
The method for manufacturing a circuit board of the present invention
(1) A step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material.
(2) A step of laminating the resin sheet of the present invention on a base material with a wiring layer and heat-curing it to form an insulating layer so that the wiring layer is embedded in the resin composition layer.
(3) Includes a step of connecting wiring layers between layers. Further, the method for manufacturing a circuit board may include (4) a step of removing the base material.

The step (3) is not particularly limited as long as the wiring layers can be interconnected between layers, but is a step of forming a via hole in the insulating layer to form the wiring layer, and a step of polishing or grinding the insulating layer to expose the wiring layer. It is preferable that the step is at least one of the above steps.

<Process (1)>
The step (1) is a step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material. Usually, the base material with a wiring layer has a first metal layer and a second metal layer, which are a part of the base material, on both sides of the base material in this order, which is opposite to the surface of the second metal layer on the base material side. A wiring layer is formed on the side surface. Specifically, a dry film (photosensitive resist film) is laminated on a base material, and exposed and developed under predetermined conditions using a photomask to form a pattern dry film. A wiring layer is formed by an electrolytic plating method using the developed pattern dry film as a plating mask, and then the pattern dry film is peeled off. The first metal layer and the second metal layer may not be provided.

Examples of the substrate include a glass epoxy substrate, a metal substrate (stainless steel, cold rolled steel plate (SPCC), etc.), a polyester substrate, a polyimide substrate, a BT resin substrate, a heat-curable polyphenylene ether substrate, and the like. A metal layer such as copper foil may be formed on the surface. Further, a metal layer such as a peelable first metal layer and a second metal layer (for example, an ultrathin copper foil with a carrier copper foil of Mitsui Kinzoku, trade name "Micro Tin") may be formed on the surface.

The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, and for example, a dry film such as a novolak resin or an acrylic resin can be used. A commercially available product may be used as the dry film.

The laminating conditions of the base material and the dry film are the same as the conditions for laminating the resin sheet in the step (2) described later so as to be embedded in the wiring layer, and the preferable range is also the same.

After laminating the dry film on the substrate, exposure and development are performed under predetermined conditions using a photomask in order to form a desired pattern on the dry film.

The line (circuit width) / space (width between circuits) ratio of the wiring layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10 μm or less, and further preferably 5 /. It is 5 μm or less, more preferably 1/1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch does not have to be the same throughout the wiring layer. The minimum pitch of the wiring layer may be 40 μm or less, 36 μm or less, or 30 μm or less.

After forming the pattern of the dry film, a wiring layer is formed and the dry film is peeled off. Here, the formation of the wiring layer can be carried out by a plating method using a dry film having a desired pattern formed as a plating mask.

The conductor material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The wiring layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). Nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of wiring layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a monometal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable. A metal layer is more preferred.

The thickness of the wiring layer depends on the desired wiring board design, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 to 20 μm, or 15 to 20 μm. When the step of polishing or grinding the insulating layer and exposing the wiring layer to interconnect the wiring layer in the step (3) is adopted, it is preferable that the thickness of the wiring to be interconnected and the thickness of the wiring not to be connected are different. .. The thickness of the wiring layer can be adjusted by repeating the above-mentioned pattern formation. The thickness of the thickest wiring layer (conductive pillar) among the wiring layers depends on the desired wiring board design, but is preferably 2 μm or more and 100 μm or less. Further, the wiring connected between layers may be convex.

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

<Process (2)>
The step (2) is a step of laminating the resin sheet of the present invention on a base material with a wiring layer so that the wiring layer is embedded in the resin composition layer, and heat-curing the resin sheet to form an insulating layer. For details, the wiring layer of the base material with the wiring layer obtained in the above-mentioned step (1) is laminated so as to be embedded in the resin composition layer of the resin sheet, and the resin composition layer of the resin sheet is thermoset and insulated. Form a layer.

Lamination of the wiring layer and the resin sheet can be performed by, for example, heat-pressing the resin sheet to the wiring layer from the support side after removing the protective film of the resin sheet. Examples of the member for heat-pressing the resin sheet to the wiring layer (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the wiring layer.

The wiring layer and the resin sheet may be laminated by a vacuum laminating method after removing the protective film of the resin sheet. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 13 hPa or less.

After laminating, the laminated resin sheet may be smoothed by pressing the heat-bonded member from the support side under normal pressure (under atmospheric pressure), for example. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

After laminating the resin composition layer on the base material with the wiring layer so that the wiring layer is embedded, the resin composition layer is thermoset to form an insulating layer. For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition and the like, but the curing temperature can be in the range of 120 ° C. to 240 ° C. and the curing time can be in the range of 5 minutes to 120 minutes. The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured.

The support of the resin sheet may be peeled off after the resin sheet is laminated on the base material with the wiring layer and thermosetting, or the support may be peeled off before the resin sheet is laminated on the base material with the wiring layer. Good. Further, the support may be peeled off before the roughening treatment step described later.

After the resin composition layer is thermoset to form an insulating layer, the surface of the insulating layer may be polished. The polishing method is not particularly limited, and polishing may be performed by a known method. For example, the surface of the insulating layer can be polished using a surface grinder.

<Process (3)>
The step (3) is a step of connecting the wiring layers between layers. The details are a step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers between layers. Alternatively, it is a step of polishing or grinding the insulating layer to expose the wiring layer and connecting the wiring layers between layers. The conductor layer is sometimes called a wiring layer.

When a step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers to each other is adopted, the formation of the via hole is not particularly limited, and laser irradiation, etching, mechanical drilling, etc. can be mentioned. It is preferably done by. This laser irradiation can be performed by using an arbitrary suitable laser processing machine that uses a carbon dioxide gas laser, a YAG laser, an excimer laser, or the like as a light source. Specifically, laser irradiation is performed from the surface side of the support of the resin sheet to form a via hole that penetrates the support and the insulating layer to expose the wiring layer.

The conditions of laser irradiation are not particularly limited, and laser irradiation can be carried out by any suitable step according to a conventional method according to the selected means.

The shape of the via hole, that is, the shape of the contour of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular).

After forming the via hole, a so-called desmear step, which is a smear removing step in the via hole, may be performed. When the conductor layer to be described later is formed by a plating step, the via hole may be subjected to, for example, a wet desmear treatment, and when the conductor layer is formed by a sputtering step, for example, a plasma treatment step or the like may be performed. A dry desmear step may be performed. Further, the desmear step may also serve as a roughening treatment step.

Before forming the conductor layer, the via hole and the insulating layer may be roughened. For the roughening treatment, known procedures and conditions that are usually performed can be adopted. Examples of the dry roughening treatment include plasma treatment, and examples of the wet roughening treatment include a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Can be mentioned.

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

After forming the via hole, 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 conventionally known suitable method such as plating, sputtering, and vapor deposition, and is preferably formed by plating. In one preferred embodiment, the surface of the insulating layer can be plated by, for example, a conventionally known technique such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. Of these, the semi-additive method is preferable. Further, when the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method. The conductor layer may have a single-layer structure, a single metal layer made of different types of metals or alloys, or a multi-layer structure in which two or more alloy layers are laminated.

When it is formed by plating, specifically, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. An electrolytic plating layer is formed by electrolytic plating on the exposed plating seed layer. At that time, along with the formation of the electrolytic plating layer, the via hole may be embedded by electrolytic plating to form a filled via. After forming the electroplating layer, the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern. When forming the conductor layer, the dry film used for forming the mask pattern is the same as the above-mentioned dry film.

The conductor layer may include not only linear wiring but also, for example, an electrode pad (land) on which an external terminal can be mounted. Further, the conductor layer may be composed of only the electrode pads.

Further, the conductor layer may be formed by forming an electrolytic plating layer and a filled via without using a mask pattern after forming the plating seed layer, and then performing patterning by etching.

When the step of polishing or grinding the insulating layer to expose the wiring layer and connecting the wiring layers to each other is adopted, the method of polishing or grinding the insulating layer is such that the wiring layer can be exposed and the polished or ground surface can be exposed. As long as it is horizontal, a conventionally known polishing method or grinding method can be applied. For example, a chemical machine polishing method using a chemical machine polishing device, a mechanical polishing method such as a buff, or a surface grinding method by rotating a grindstone. And so on. Similar to the step of forming a via hole in the insulating layer, forming the conductor layer, and connecting the wiring layers between layers, a smear removing step and a roughening treatment step may be performed, or a conductor layer may be formed. Further, it is not necessary to expose all the wiring layers, and a part of the wiring layers may be exposed.

<Process (4)>
Step (4) is a step of removing the base material and forming the circuit board of the present invention. The method for removing the base material is not particularly limited. In one preferred embodiment, the base material is peeled off from the circuit board at the interface between the first and second metal layers, and the second metal layer is removed by etching with, for example, an aqueous solution of copper chloride. If necessary, the base material may be peeled off with the conductor layer protected by a protective film.

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

[Semiconductor chip package]
The first aspect of the semiconductor chip package of the present invention is a semiconductor chip package in which a semiconductor chip is mounted on the circuit board. A semiconductor chip package can be manufactured by joining a semiconductor chip to the circuit board.

As long as the terminal electrode of the semiconductor chip is connected to the circuit wiring of the circuit board by a conductor, the bonding conditions are not particularly limited, and known conditions used in flip chip mounting of the semiconductor chip may be used. Further, the semiconductor chip and the circuit board may be bonded to each other via an insulating adhesive.

In one preferred embodiment, the semiconductor chip is crimped onto the circuit board. As the crimping conditions, for example, the crimping 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 crimping time is in the range of 1 second to 60 seconds. (Preferably 5 to 30 seconds).

Further, in another preferred embodiment, the semiconductor chip is reflowed and joined to the circuit board. The reflow condition can be, for example, in the range of 120 ° C. to 300 ° C.

It is also possible to obtain a semiconductor chip package by joining the semiconductor chip to a circuit board and then filling the semiconductor chip with a mold underfill material, for example. The method of filling with the mold underfill material can be carried out by a known method. The resin composition or resin sheet of the present invention can also be used as a mold underfill material.

A 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 FIG. 1 as an example. The semiconductor chip package (Fan-out type WLP) 100 as shown in FIG. 1 is a semiconductor chip package in which the sealing layer 120 is manufactured from the resin composition or resin sheet of the present invention. The semiconductor chip package 100 is rewired on the surface of the semiconductor chip 110, the sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110, and the side opposite to the side covered by the sealing layer of the semiconductor chip 110. A layer (insulating layer) 130, a conductor layer (rewiring layer) 140, a solder resist layer 150, and bumps 160 are provided. The manufacturing method of such a semiconductor chip package is
(A) Step of laminating a temporary fixing film on a base material,
(B) A process of temporarily fixing a semiconductor chip on a temporary fixing film,
(C) A step of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip, or applying the resin composition of the present invention on a semiconductor chip and thermosetting to form a sealing layer.
(D) Step of peeling the base material and the temporary fixing film from the semiconductor chip,
(E) A step of forming a rewiring forming layer (insulating layer) on the surface from which the base material and the temporary fixing film of the semiconductor chip are peeled off.
It includes (F) a step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer), and (G) a step of forming a solder resist layer on the conductor layer. Further, the method for manufacturing a semiconductor chip package may include (H) a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and separating them into individual pieces.

<Process (A)>
The step (A) is a step of laminating a temporary fixing film on the base material. The laminating conditions of the base material and the temporary fixing film are the same as the laminating conditions of the wiring layer and the resin sheet in the step (2) in the method of manufacturing the circuit board, and the preferable range is also the same.

The material used for the base material is not particularly limited. As the base material, silicon wafer; glass wafer; glass substrate; metal substrate such as copper, titanium, stainless steel, cold rolled steel plate (SPCC); glass fiber such as FR-4 substrate is impregnated with epoxy resin or the like and heat-cured. Substrate; Examples thereof include a substrate made of bismaleimide triazine resin such as BT resin.

The material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in the step (D) described later and the semiconductor chip can be temporarily fixed. A commercially available product can be used as the temporary fixing film. Examples of commercially available products include Riva Alpha manufactured by Nitto Denko Corporation.

<Process (B)>
The step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. Temporary fixing of the semiconductor chip can be performed using a known device such as a flip chip bonder or a die bonder. The layout and number of arrangements of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, and the like. For example, a matrix having a plurality of rows and a plurality of columns. It can be arranged in a shape and temporarily fixed.

<Process (C)>
The step (C) is a step of laminating the resin composition layer of the resin sheet of the present invention on a semiconductor chip, or applying the resin composition of the present invention on a semiconductor chip and thermosetting to form a sealing layer. Is. In the step (C), it is preferable that the resin composition layer of the resin sheet is laminated on the semiconductor chip and heat-cured to form a sealing layer.

Lamination of the semiconductor chip and the resin sheet can be performed by, for example, heat-pressing the resin sheet to the semiconductor chip from the support side after removing the protective film of the resin sheet. Examples of the member for heat-pressing the resin sheet to the semiconductor chip (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable not to press the heat-bonded member directly onto the resin sheet, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the semiconductor chip.

Further, the semiconductor chip and the resin sheet may be laminated by a vacuum laminating method after removing the protective film of the resin sheet. The laminating conditions in the vacuum laminating method are the same as the laminating conditions for the wiring layer and the resin sheet in the step (2) in the method for manufacturing the circuit board, and the preferable range is also the same.

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

The coating conditions for the resin composition are the same as the coating conditions for forming the resin composition layer in the resin sheet of the present invention, and the preferable range is also the same.

<Process (D)>
The step (D) is a step of peeling the base material and the temporary fixing film from the semiconductor chip. The method of peeling can be appropriately changed depending on the material of the temporary fixing film, for example, a method of heating, foaming (or expanding) the temporary fixing film to peel it off, and irradiating ultraviolet rays from the base material side. Examples thereof include a method of reducing the adhesive strength of the temporary fixing film and peeling it off.

In the method of heating, foaming (or expanding) and peeling off the temporary fixing film, the heating conditions are usually 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. Also, by irradiating ultraviolet rays from the substrate side, in the method for peeling to lower the adhesive strength of the temporary fixing film, dose of the ultraviolet rays is ^{usually, 10mJ / cm 2 ~1000mJ / cm} 2.

<Process (E)>
The step (E) is a step of forming a rewiring forming layer (insulating layer) on the surface from which the base material and the temporary fixing film of the semiconductor chip have been peeled off.

The material for forming the rewiring forming layer (insulating layer) is not particularly limited as long as it has insulating properties when the rewiring forming layer (insulating layer) is formed, and from the viewpoint of ease of manufacturing a semiconductor chip package, it is considered. Photosensitive resin and thermosetting resin are preferable. As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention may be used.

After forming the rewiring forming layer (insulating layer), via holes may be formed in the rewiring forming layer (insulating layer) in order to interconnect the semiconductor chip and the conductor layer described later.

When forming the via hole, when the material for forming the rewiring cambium (insulating layer) is a photosensitive resin, first, the surface of the rewiring cambium (insulating layer) is irradiated with active energy rays through a mask pattern. The most wiring layer of the part is photocured.

Examples of the active energy ray include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are particularly preferable. The irradiation amount and irradiation time of ultraviolet rays can be appropriately changed depending on the photosensitive resin. The exposure methods include a contact exposure method in which the mask pattern is brought into close contact with the rewiring cambium (insulating layer) and exposed, and an exposure method using parallel light rays without bringing the mask pattern into close contact with the rewiring cambium (insulating layer). Any non-contact exposure method may be used.

Next, the rewiring forming layer (insulating layer) is developed and the unexposed portion is removed to form a via hole. Both wet development and dry development are suitable for development. A known developer can be used as the developer used in wet development.

Examples of the developing method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and the paddle method is preferable from the viewpoint of resolution.

When the material for forming the rewiring forming layer (insulating layer) is a thermosetting resin, the formation of via holes is not particularly limited, and examples thereof include laser irradiation, etching, and mechanical drilling, which can be performed by laser irradiation. preferable. Laser irradiation can be performed using an arbitrary suitable laser processing machine that uses a carbon dioxide gas laser, a UV-YAG laser, an excimer laser, or the like as a light source.

The conditions of laser irradiation are not particularly limited, and laser irradiation can be carried out by any suitable step according to a conventional method according to the selected means.

The shape of the via hole, that is, the shape of the contour of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole (diameter of the opening on the surface of the rewiring forming layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 20 μm or less. The lower limit is not particularly limited, but is preferably 10 μm or more, more preferably 15 μm or more, and further preferably 20 μm or more.

<Process (F)>
The step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring forming layer (insulating layer). The method of forming the conductor layer on the rewiring forming layer (insulating layer) is the same as the method of forming the conductor layer after forming the via hole in the insulating layer in the step (3) in the method of manufacturing the circuit board, which is preferable. The range is similar. The steps (E) and (F) may be repeated, and the conductor layer (rewiring layer) and the rewiring forming layer (insulating layer) may be alternately stacked (build-up).

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

The material for forming the solder resist layer is not particularly limited as long as it has an insulating property at the time of forming the solder resist layer, and a photosensitive resin or a thermosetting resin is preferable from the viewpoint of ease of manufacturing a semiconductor chip package. .. As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention may be used.

Further, in the step (G), bumping may be performed to form bumps, if necessary. The bumping process can be performed by a known method such as solder balls and solder plating. Further, the formation of the via hole in the bumping process can be performed in the same manner as in the step (E).

<Process (H)>
The method for manufacturing a semiconductor chip package may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and individualizing them.

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

A third aspect of the semiconductor chip package of the present invention includes, for example, a rewiring forming layer (insulating layer) 130 and a solder resist layer 150 in a semiconductor chip package (Fan-out type WLP) as shown in FIG. A semiconductor chip package manufactured from the resin composition or resin sheet of the present invention.

[Semiconductor device]
Semiconductor devices to which the semiconductor chip package of the present invention is mounted include electric products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, televisions, etc.) and vehicles (for example). For example, various semiconductor devices used in motorcycles, automobiles, trains, ships, aircraft, etc.) can be mentioned.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" representing quantities mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Preparation of sample for peel strength measurement>
(1) Base treatment of inner layer circuit board Both sides of the glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Panasonic R5715ES) on which the inner layer circuit is formed are manufactured by MEC. The copper surface was roughened by immersing it in CZ8100.

(2) Lamination of Resin Sheets The resin sheets produced in Examples and Comparative Examples were subjected to a resin composition layer using a batch type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.). It was laminated on both sides of the inner layer circuit board so as to be joined to the inner layer circuit board. Lamination was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Then, heat pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds. The obtained laminated board with a resin composition layer was heat-treated at 180 ° C. for 30 minutes to cure the resin composition layer to obtain a laminated board with a cured product.

(3) Roughening treatment The obtained laminated board with a cured product was immersed in Swelling Dip Securigan P (swelling liquid) containing diethylene glycol monobutyl ether manufactured by Atotech Japan at 60 ° C. for 5 minutes, and then Atotech Japan. Immerse in Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution, neutralized solution) manufactured by Atotech Japan Co., Ltd. at 80 ° C. for 10 minutes, and finally, Atotech Japan Co., Ltd. The surface of the cured product was roughened by immersing it in Gant P (neutralizing solution) at 40 ° C. for 5 minutes. The laminated board obtained by the roughening treatment was used as the evaluation substrate A.

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

<Measurement and evaluation of peeling strength (peeling strength) of metal layer>
Make a notch in the metal layer of the evaluation substrate B with a width of 10 mm and a length of 100 mm, and peel off one end of the notch (autocom type testing machine "AC-50C-SL" manufactured by TSE). The peel strength was determined by measuring the load (kgf / cm) when 20 mm was peeled off in the vertical direction at a speed of 50 mm / min at room temperature.

<Preparation of cured product for elastic modulus evaluation>
The untreated surface of the release PET film (Lintech "501010", thickness 38 μm, 240 mm square) is a glass cloth base material epoxy resin double-sided copper-clad laminate (Matsushita Electric Works "R5715ES", thickness 0.7 mm, It was placed on a glass cloth-based epoxy resin double-sided copper-clad laminate so as to be in contact with (255 mm square), and the four sides of the release PET film were fixed with polyimide adhesive tape (width 10 mm).

Each resin sheet (167 × 107 mm square) produced in Examples and Comparative Examples was subjected to a resin composition layer using a batch type vacuum pressurizing laminator (2-stage build-up laminator manufactured by Nikko Materials Co., Ltd., CVP700). It was laminated in the center so as to be in contact with the release surface of the release PET film. The laminating treatment was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

Then, the support was peeled off, and the resin composition layer was heat-cured at 180 ° C. for 90 minutes.

After thermosetting, the polyimide adhesive tape was peeled off, and the resin composition layer was removed from the glass cloth-based epoxy resin double-sided copper-clad laminate. Further, the release PET film was peeled off from the resin composition layer to obtain a sheet-shaped cured product (evaluation cured product).

<Measurement of elastic modulus>
The cured product for evaluation was cut into a dumbbell-shaped No. 1 shape to obtain a test piece. The test piece was subjected to tensile strength measurement using a tensile tester "RTC-1250A" manufactured by Orientec, and the elastic modulus at 23 ° C. was determined. The measurement was carried out in accordance with JIS K7127. This operation was performed three times, and the average value is shown in the table.

<Evaluation of warpage amount>
The resin sheet produced in Examples and Comparative Examples was used as a glass cloth base material BT resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.15 mm, Mitsubishi Gas Chemical Company “HL832NSF LCA”, size 15 cm × 18 cm. ) Is laminated with a batch type vacuum pressurizing laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), and after removing the release PET, heat at 100 ° C for 30 minutes and then at 180 ° C for 30 minutes. It was cured and placed on a flat surface to check the amount of warpage. The average value of the amount of warpage of each of the four corners was "○" for less than 1 cm, "Δ" for 1-2 cm, and "x" for 2 cm or more.

<Measurement of thermal conductivity of cured product>
(1) Preparation of cured product sample PET film ("Lumilar R80" manufactured by Toray Co., Ltd.) obtained by releasing the resin varnish produced in Examples and Comparative Examples with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation). (Thickness 38 μm, softening point 130 ° C.), apply with a die coater so that the thickness of the resin composition layer after drying is 100 μm, and dry at 80 ° C. to 100 ° C. (average 90 ° C.) for 7 minutes. Obtained a resin composition layer.

Using a batch type vacuum pressurizing laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), three resin composition layers are laminated, then laminated, and cured at 180 ° C. for 90 minutes. The resin composition layer was cured with, and a cured product sample was obtained. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.4 MPa for 20 seconds.

(2) Measurement of Thermal Diffusivity α For the cured product sample, the thermal diffusivity α (m ² / s) in the thickness direction of the cured product sample was measured using “ai-Phase Mobile 1u” manufactured by ai-Phase. It was measured by the temperature wave analysis method. The same sample was measured three times and the average value was calculated.

(3) Measurement of specific heat capacity Cp A cured sample is measured by raising the temperature from -40 ° C to 80 ° C at 10 ° C / min using a differential scanning calorimeter (“DSC7020” manufactured by SII Nanotechnology). The specific heat capacity Cp (J / kg · K) of the cured product sample at 25 ° C. was calculated.

(4) Measurement of Density ρ The density (kg / m ³ ) of the cured product sample was measured using an analytical balance XP105 (using a specific gravity measurement kit) manufactured by METTLER TOLEDO.

(5) Calculation of thermal conductivity λ The thermal diffusivity α (m ² / s), the specific heat capacity Cp (J / kg · K), and the density ρ (kg / m) obtained in (2) to (4) above. ^By substituting ³ ) into the following formula (I), the thermal conductivity λ (W / m · K) was calculated.
λ = α × Cp × ρ (I)

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

<Synthesis Example 1: Synthesis of Polymer Compound 1>
69 g of G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g / eq., Solid content 100% by mass: manufactured by Nippon Soda Co., Ltd.) and ipzol 150 in a reaction vessel. (Aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petroleum Chemical Co., Ltd.) 40 g and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 50 ° C., and 8 g of isophorone diisocyanate (IPDI, isocyanate group equivalent = 113 g / eq.) Manufactured by Evonik Degussa Japan Co., Ltd. was added with further stirring, and the reaction was carried out for about 3 hours. Next, the reaction product is cooled to room temperature, and then 23 g of a cresol novolak resin (KA-1160, manufactured by DIC, hydroxyl group equivalent = 117 g / eq.) And 60 g of ethyldiglycol acetate (manufactured by Daicel) are added thereto. The temperature was raised to 80 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak of 2250 cm ^-1 was confirmed from FT-IR. Confirmation of the disappearance of the NCO peak is regarded as the end point of the reaction, and the reaction product is cooled to room temperature and then filtered through a filter cloth having a size of 100 μm. Polymer compound 1 having a polybutadiene structure and a phenolic hydroxyl group (nonvolatile content: 50% by mass) Got

<Synthesis Example 2: Synthesis of Polymer Compound 2>
80 g of polycarbonate diol (number average molecular weight: about 1,000, hydroxyl group equivalent: 500, non-volatile content: 100%, "C-1015N" manufactured by Kuraray Co., Ltd.) and 0.01 g of dibutyltin dilaurate are placed in a reaction vessel with diethylene glycol monoethyl ether. It was uniformly dissolved in 37.6 g of acetate (“ethyl diglycol acetate” manufactured by Daicel). Then, the temperature of the mixture was raised to 50 ° C., and 27.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent: 87.08) was added with further stirring, and the reaction was carried out for about 3 hours. The reaction is then cooled to room temperature and then to which 14.3 g of benzophenonetetracarboxylic dianhydride (acid anhydride equivalent: 161.1), 0.12 g of triethylenediamine, and diethylene glycol monoethyl ether acetate (Dycel). 84.0 g of "ethyldiglycol acetate" manufactured by the same company was added, the temperature was raised to 130 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak of 2250 cm ^-1 was confirmed from FT-IR. Confirmation of the disappearance of the NCO peak is regarded as the end point of the reaction, and the reaction product is cooled to room temperature and then filtered through a filter cloth having a mesh size of 100 μm to obtain polymer compound 2 having a carbonate structure (nonvolatile content: 50% by mass). Obtained.

<Measurement of average particle size of thermally conductive filler>
To a 20 ml vial, add 0.01 g of a heat conductive filler, 0.2 g of a nonionic dispersant (“T208.5” manufactured by Nippon Oil & Fats Co., Ltd.), and 10 g of pure water, and ultrasonically disperse for 10 minutes with an ultrasonic cleaner. Was performed to prepare a sample. Next, the sample was put into a laser diffraction type particle size distribution measuring device (“SALD2200” manufactured by Shimadzu Corporation), and ultrasonic waves were irradiated for 10 minutes while circulating. After that, the ultrasonic waves were stopped, the particle size distribution was measured while maintaining the circulation of the sample, and the average particle size of the heat conductive filler was determined. The refractive index at the time of measurement was set to 1.45-0.001i.

<Measurement of specific surface area of thermally conductive filler>
The specific surface area was determined by the nitrogen BET method using an automatic specific surface area measuring device (“Macsorb HM-1210” manufactured by Mountech Co., Ltd.).

<Thermal conductive filler used>
Alumina 1: A mixture of alumina with different average particle size and specific surface area, average particle size 3 μm, specific surface area 1.5 m ² / g, “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Alumina 2: A mixture of alumina with different average particle size and specific surface area, average particle size 3 μm, specific surface area 1.5 m ² / g, “KBM5783” (N-phenyl-3-amino) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Surface-treated with octyltrimethoxysilane) Alumina 3: A mixture of alumina with different average particle size and specific surface area, average particle size 3 μm, specific surface area 1.5 m ² / g, “KBM403” (3-) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Surface-treated with glycidoxypropyltrimethoxysilane) Alumina 4: A mixture of alumina with different average particle size and specific surface area, average particle size 3 μm, specific surface area 1.5 m ² / g, “KBM903” manufactured by Shin-Etsu Chemical Industry Co., Ltd. Surface-treated with (3-aminopropyltrimethoxysilane)

<Example 1>
Aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g / eq) 6 parts, 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: 169 g / eq) 5 parts, bixilenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000H", epoxy equivalent: 185 g / eq) 2 parts, biphenyl type epoxy resin (Japan "NC3100" manufactured by Kayakusha, epoxy equivalent: 258 g / eq) 2 parts dissolved in 10 parts of methyl ethyl ketone, alumina 1 270 parts, polymer compound 1 (solid content 50% by mass, number average molecular weight 5500) 24 parts, Active ester hardener ("HPC-8000-65T" manufactured by DIC, active ester equivalent 223 g / eq, toluene solution with 65% solid content), 3 parts, solid naphthol hardener ("SN485" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 2 parts of hydroxyl group equivalent 215 g / eq, used as a methyl ethyl ketone solution with a solid content of 50%, 1 part of a curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with a solid content of 10% by mass), 15 parts of methyl ethyl ketone was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 1.

PET film ("Lumilar R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., "Release PET"" obtained by releasing the resin varnish 1 with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation). On top of this, a die coater is applied so that the thickness of the resin composition layer after drying is 50 μm, and the resin sheet 1 is dried at 80 ° C. to 100 ° C. (average 90 ° C.) for 5 minutes. Obtained.

<Example 2>
Aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g / eq) 6 parts, 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: 169 g / eq) 5 parts, bixilenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000H", epoxy equivalent: 185 g / eq) 2 parts, biphenyl type epoxy resin (Japan "NC3100" manufactured by Kayakusha, epoxy equivalent: 258 g / eq) 2 parts dissolved in 10 parts of methyl ethyl ketone, alumina 1 270 parts, polymer compound 1 (solid content 50% by mass, number average molecular weight 5500) 24 parts, Active ester hardener ("HPC-8000-65T" manufactured by DIC, active ester equivalent 223 g / eq, toluene solution with 65% solid content), 6 parts, solid naphthol hardener ("SN485" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 6 parts of hydroxyl group equivalent 215 g / eq, used as methyl ethyl ketone solution with 50% solid content, 1 part of curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with 10% by mass solid content), Fifteen parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 2. Further, in Example 1, a resin sheet 2 was obtained in the same manner as in Example 1 except that the resin varnish 1 was changed to the resin varnish 2.

<Example 3>
Aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g / eq) 6 parts, 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: 169 g / eq) 5 parts, bixilenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000H", epoxy equivalent: 185 g / eq) 2 parts, biphenyl type epoxy resin (Japan 2 parts of "NC3100" manufactured by Kayakusha Co., Ltd., epoxy equivalent: 258 g / eq) 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, active ester equivalent 223 g / eq, toluene solution with 65% solid content), 3 parts, solid naphthol hardener ("SN485" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 2 parts of hydroxyl group equivalent 215 g / eq, used as a methyl ethyl ketone solution with a solid content of 50%, 1 part of a curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with a solid content of 10% by mass), 15 parts of methyl ethyl ketone was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 3. Further, in Example 1, a resin sheet 3 was obtained in the same manner as in Example 1 except that the resin varnish 1 was changed to the resin varnish 3.

<Example 4>
Aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g / eq) 6 parts, 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: 169 g / eq) 5 parts, bixilenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000H", epoxy equivalent: 185 g / eq) 2 parts, biphenyl type epoxy resin (Japan "NC3100" manufactured by Kayakusha, epoxy equivalent: 258 g / eq) 2 parts dissolved in 10 parts of methyl ethyl ketone, alumina 2 270 parts, polymer compound 1 (solid content 50% by mass, number average molecular weight 5500) 24 parts, Active ester hardener ("HPC-8000-65T" manufactured by DIC, active ester equivalent 223 g / eq, toluene solution with 65% solid content), 3 parts, solid naphthol hardener ("SN485" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 2 parts of hydroxyl group equivalent 215 g / eq, used as a methyl ethyl ketone solution with a solid content of 50%, 1 part of a curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with a solid content of 10% by mass), Fifteen parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 4. Further, in Example 1, a resin sheet 4 was obtained in the same manner as in Example 1 except that the resin varnish 1 was changed to the resin varnish 4.

<Example 5>
Aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g / eq) 6 parts, 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: 169 g / eq) 5 parts, bixilenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000H", epoxy equivalent: 185 g / eq) 2 parts, biphenyl type epoxy resin (Japan "NC3100" manufactured by Kayakusha, epoxy equivalent: 258 g / eq) 2 parts dissolved in 10 parts of methyl ethyl ketone, 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, active ester equivalent 223 g / eq, toluene solution with 65% solid content), 3 parts, solid naphthol hardener ("SN485" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 2 parts of hydroxyl group equivalent 215 g / eq, used as a methyl ethyl ketone solution with a solid content of 50%, 1 part of a curing accelerator (2-phenyl-1-benzyl-1H-imidazole (1B2PZ), MEK solution with a solid content of 10% by mass), 15 parts of methyl ethyl ketone was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 5. Further, in Example 1, a resin sheet 5 was obtained in the same manner as in Example 1 except that the resin varnish 1 was changed to the resin varnish 4.

<Comparative example 1>
Aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g / eq) 6 parts, 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: 169 g / eq) 5 parts, bixilenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000H", epoxy equivalent: 185 g / eq) 2 parts, biphenyl type epoxy resin (Japan "NC3100" manufactured by Kayakusha, epoxy equivalent: 258 g / eq) 2 parts dissolved in 10 parts of methyl ethyl ketone, alumina 1 270 parts, polymer compound 1 (solid content 50% by mass, number average molecular weight 5500) 24 parts, Solid naphthol-based curing agent (“SN485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., used as a methyl ethyl ketone solution with a hydroxyl group equivalent of 215 g / eq and a solid content of 50%), 6 parts, curing accelerator (2-phenyl-1-benzyl-1H-imidazole) (1B2PZ), MEK solution having a solid content of 10% by mass) and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 6. Further, in Example 1, a resin sheet 6 was obtained in the same manner as in Example 1 except that the resin varnish 1 was changed to the resin varnish 6.

<Comparative example 2>
Aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g / eq) 6 parts, 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: 169 g / eq) 5 parts, bixilenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000H", epoxy equivalent: 185 g / eq) 2 parts, biphenyl type epoxy resin (Japan "NC3100" manufactured by Kayakusha, epoxy equivalent: 258 g / eq) 2 parts dissolved in 10 parts of methyl ethyl ketone, alumina 1 270 parts, polymer compound 1 (solid content 50% by mass, number average molecular weight 5500) 26 parts, Solid naphthol-based curing agent (“SN485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., used as a methyl ethyl ketone solution with a hydroxyl group equivalent of 215 g / eq and a solid content of 50%), 2 parts, curing accelerator (2-phenyl-1-benzyl-1H-imidazole) (1B2PZ), MEK solution having a solid content of 10% by mass) and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 7. Further, in Example 1, a resin sheet 7 was obtained in the same manner as in Example 1 except that the resin varnish 1 was changed to the resin varnish 7.

<Comparative example 3>
Aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g / eq) 6 parts, 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: 169 g / eq) 5 parts, bixilenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000H", epoxy equivalent: 185 g / eq) 2 parts, biphenyl type epoxy resin (Japan "NC3100" manufactured by Kayakusha, epoxy equivalent: 258 g / eq) 2 parts dissolved in 10 parts of methyl ethyl ketone, alumina 3 270 parts, polymer compound 1 (solid content 50% by mass, number average molecular weight 5500) 24 parts, Solid naphthol-based curing agent (“SN485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., used as a methyl ethyl ketone solution with a hydroxyl group equivalent of 215 g / eq and a solid content of 50%), 6 parts, curing accelerator (2-phenyl-1-benzyl-1H-imidazole) (1B2PZ), MEK solution having a solid content of 10% by mass) and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 8. Further, in Example 1, a resin sheet 8 was obtained in the same manner as in Example 1 except that the resin varnish 1 was changed to the resin varnish 8.

<Comparative example 4>
Aminophenol type epoxy resin ("630" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 95g / eq) 6 parts, 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: 169 g / eq) 5 parts, bixilenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000H", epoxy equivalent: 185 g / eq) 2 parts, biphenyl type epoxy resin (Japan "NC3100" manufactured by Kayakusha, epoxy equivalent: 258 g / eq) 2 parts dissolved in 10 parts of methyl ethyl ketone, alumina 4 270 parts, polymer compound 1 (solid content 50% by mass, number average molecular weight 5500) 24 parts, Solid naphthol-based curing agent (“SN485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., used as a methyl ethyl ketone solution with a hydroxyl group equivalent of 215 g / eq and a solid content of 50%), 6 parts, curing accelerator (2-phenyl-1-benzyl-1H-imidazole) (1B2PZ), MEK solution having a solid content of 10% by mass) and 15 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 9. Further, in Example 1, a resin sheet 9 was obtained in the same manner as in Example 1 except that the resin varnish 1 was changed to the resin varnish 9.

The abbreviations in the table below are as follows.
Polymer 1: Polymer compound produced in Synthesis Example 1 Polymer 2: Polymer compound produced in Synthesis Example 630: Aminophenol type epoxy resin, epoxy equivalent: 95 g / eq, Mitsubishi Chemical Co., Ltd. ZX1059: Bisphenol A type 1: 1 mixture (mass ratio) of epoxy resin and bisphenol F type epoxy resin, epoxy equivalent: 169 g / eq, YX4000H manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd .: Bixylenol type epoxy resin, epoxy equivalent: 185 g / eq, Mitsubishi Chemical Co., Ltd. NC3100: Biphenyl type epoxy resin, epoxy equivalent: 258 g / eq, Nippon Kayaku Co., Ltd. Alumina 1: A mixture of alumina with different average particle size and specific surface area, average particle size 3 μm, specific surface area 1.5 m ² / g, Shinetsu Surface-treated with "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Kagaku Kogyo Co., Ltd. Alumina 2: A mixture of alumina with different average particle size and specific surface area, average particle size 3 μm, specific surface area 1.5 m ² / g, surface-treated with "KBM5783" (N-phenyl-3-aminooctylrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Alumina 3: A mixture of alumina having different average particle size and specific surface area, average particle size 3 μm, Specific surface area 1.5 m ² / g, surface treated with "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. Alumina 4: A mixture of alumina with different average particle size and specific surface area, average grain Diameter 3 μm, specific surface area 1.5 m ² / g, surface treated with "KBM903" (3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd. HPC-8000-65T: Active ester hardener, active ester equivalent 223 g / eq, DIC SN485: solid naphthol-based curing agent, hydroxyl group equivalent 215 g / eq, Nippon Steel & Sumikin Chemical Co., Ltd. 1B2PZ: curing accelerator, 2-phenyl-1-benzyl-1H-imidazole, MEK with solid content of 10% by mass Content of component (A) of solution: Content when the non-volatile component of the resin composition excluding component (C) is 100% by mass Content of component (C): 100% by mass of non-volatile component of resin composition Content when

As shown in Examples 1 to 5, it can be seen that the insulating layer formed from the resin composition containing the components (A) to (D) is excellent in peel strength. On the other hand, it can be seen that the peel strengths of Comparative Examples 1 to 4 containing no component (D) are inferior to those of Examples 1 to 5. Further, it can be seen that Comparative Examples 3 to 4 in which the component (C) is not treated with N-phenyl-3-aminoalkyltrimethoxysilane have a high melt viscosity, so that the laminate property is poor and the peel strength is also poor.
It has been confirmed that even when the component (F) is not contained, the result is the same as that of the above-mentioned example, although the degree is different.

100 Semiconductor chip package 110 Semiconductor chip 120 Encapsulating layer 130 Rewiring forming layer (insulating layer)
140 Conductor layer (rewiring layer)
150 solder resist layer 160 bumps

Claims (17)

(A) One or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. Polymer compound,
(B) Epoxy resin,
Containing (C) a thermally conductive filler and (D) an active ester curing agent,
The component (A) is selected from a resin having a number average molecular weight (Mn) of 1,000 to 1,000,000 or a glass transition temperature (Tg) of 25 ° C. or lower, and a resin which is liquid at 25 ° C. Is one or more types
The content of the component (A) is 10% by mass or more and 65% by mass or less when the resin component is 100% by mass.
A resin composition in which the content of the component (C) is 85% by mass or more when the non-volatile component of the resin composition is 100% by mass. However, the case where the content of the component (C) is 85% by mass when the non-volatile component of the resin composition is 100% by mass is excluded. 30 minutes The resin composition at 180 ° C., is more 180 and cured product obtained by curing for 60 minutes heat at ° C., peel strength between the metal layer formed by plating 0.4 kgf / cm or more, according to claim 1 Resin composition. The resin composition according to claim 1 or 2 , wherein the component (C) contains alumina. The resin composition according to any one of claims 1 to 3 , wherein the component (C) is surface-treated with an aminosilane-based coupling agent. The resin composition according to any one of claims 1 to 4 , wherein the component (C) is surface-treated with N-phenyl-3-aminoalkyltrimethoxysilane. Any one of claims 1 to 5 , wherein the cured product obtained by thermally curing the resin composition at 180 ° C. for 90 minutes has a thermal conductivity of 1.5 W / m · K or more and 5.0 W / m · K or less. The resin composition according to. The resin composition according to any one of claims 1 to 6 , wherein the component (A) has a functional group capable of reacting with the component (B). The component (A) has one or more functional groups selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group, according to any one of claims 1 to 7. The resin composition described. The resin composition according to any one of claims 1 to 8 , wherein the component (A) has an imide structure. The resin composition according to any one of claims 1 to 9 , wherein the component (A) has a phenolic hydroxyl group. The resin composition according to any one of claims 1 to 10 , wherein the component (A) has a polybutadiene structure and has a phenolic hydroxyl group. The resin composition according to any one of claims 1 to 11, which is a resin composition for an insulating layer of a semiconductor chip package. The resin composition according to any one of claims 1 to 12 , which is a resin composition for an insulating layer of a circuit board in which a circuit is formed by a semi-additive process method. A support, provided on the support, a resin sheet having a resin composition layer comprising a resin composition according to any one of claims 1 to 1 3. Comprising an insulating layer formed by the cured product of the resin composition according to any one of claims 1 to 1 3, a circuit board. A semiconductor chip package including the circuit board according to claim 15 and a semiconductor chip mounted on the circuit board. A semiconductor chip package including a semiconductor chip sealed by resin sheet according to claim 1 to 1 resin composition according to any one of 3 or claim 1 4,.

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