JP7067594B2 - Resin composition - Google Patents

Description

The present invention relates to a resin composition. Further, 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 in printed wiring boards tends to increase. Along with the high functionality of the mounted semiconductor element, there is a demand for a technique for efficiently diffusing the heat generated by the semiconductor element.

For example, Patent Document 1 discloses that heat is diffused by using an insulating layer obtained by curing a high thermal conductive resin composition containing a resin and an inorganic filler having a specific average particle size for a printed wiring board. Has been done.

Japanese Unexamined Patent Publication No. 2013-189625

The present inventors have investigated the thermal conductivity of the insulating layer in order to diffuse the heat generated by the semiconductor element more efficiently. As a result, when the resin composition containing the thermally conductive filler is cured to form an insulating layer, the thermal conductivity of the obtained insulating layer has a trade-off relationship with the adhesion strength (peel strength) to the metal layer. The present inventors have found. Specifically, by increasing the content of the heat conductive filler in the resin composition, the heat conductivity of the obtained insulating layer can be improved, but the heat conductivity is high enough to exhibit sufficient heat conductivity. It has been found that when the content of the filler is increased, the obtained insulating layer is inferior in the adhesion strength to the metal layer.

The present invention provides a resin composition capable of obtaining an insulating layer having excellent thermal conductivity and adhesion strength to a metal layer; a resin sheet, a circuit board, and a semiconductor chip package using the resin composition. ..

The present inventors have (A) a resin having one or more structures selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule, and (B) an aromatic structure. It was found that an insulating layer having excellent thermal conductivity and adhesion strength to a metal layer can be obtained by containing (C) a heat conductive filler having a predetermined average particle size and a predetermined specific surface area. , The present invention has been completed.

That is, the present invention includes the following contents.
[1] (A) A resin having one or more structures selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule.
It contains (B) an epoxy resin having an aromatic structure and (C) a thermally conductive filler.
(C) A resin composition having an average particle size of 2.5 μm to 5.0 μm and a specific surface area of 0.8 m ² / g or more.
[2] The resin composition according to [1], wherein the peel strength between the cured product obtained by thermally curing the resin composition at 180 ° C. for 90 minutes and the metal layer is 0.4 kgf / cm or more.
[3] The resin composition according to [1] or [2], wherein the cured product obtained by thermally curing the resin composition at 180 ° C. for 90 minutes and the electrolytic copper foil have a peel strength of 0.4 kgf / cm or more.
[4] The resin composition according to any one of [1] to [3], wherein the content of the component (C) is 87% by mass or more when the non-volatile component in the resin composition is 100% by mass. ..
[5] The resin composition according to any one of [1] to [4], wherein the component (C) is alumina.
[6] Of [1] to [5], 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 to 5.0 W / m · K. The resin composition according to any one.
[7] The composition according to any one of [1] to [6], 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.
[8] The resin composition according to any one of [1] to [7], wherein the component (A) has a functional group capable of reacting with the component (B).
[9] Of [1] to [8], 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.
[10] The resin composition according to any one of [1] to [9], wherein the component (A) has an imide structure.
[11] The resin composition according to any one of [1] to [10], wherein the component (A) has a phenolic hydroxyl group.
[12] The resin composition according to any one of [1] to [11], wherein the component (A) has a polybutadiene structure and a phenolic hydroxyl group.
[13] The resin composition according to any one of [1] to [12], which is a resin composition for an insulating layer of a semiconductor chip package.
[14] A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition according to any one of [1] to [13].
[15] The resin sheet according to [14], which is a resin sheet for an insulating layer of a semiconductor chip package.
[16] A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [13].
[17] A semiconductor chip package including the circuit board according to [16] and a semiconductor chip mounted on the circuit board.
[18] A semiconductor chip package containing the resin composition according to any one of [1] to [13] or a semiconductor chip sealed with the resin sheet according to [14].

According to the present invention, a resin composition capable of obtaining an insulating layer having excellent thermal conductivity and adhesion to a metal layer; a resin sheet, a circuit board, and a semiconductor chip package using the resin composition are provided. Can be done.

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 comprises (A) a resin having one or more structures selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule, and (B) aroma. It contains an epoxy resin having a group structure and (C) a thermally conductive filler, and the average particle size of the component (C) is 2.5 μm to 5.0 μm, and the specific surface area is 0.8 m ² / g or more. be.

By incorporating the component (A), the component (B), and the component (C) having a predetermined average particle size and a predetermined specific surface area into the resin composition, an insulating layer having excellent thermal conductivity and peel strength with respect to the metal layer is provided. Can be obtained. The resin composition further contains (D) a curing agent, (E) a curing accelerator, (F) an inorganic filler (excluding those corresponding to the component (C)) and (G) a flame retardant, if necessary. obtain. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) A resin having one or more structures selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule>
The resin composition of the present invention contains, as the component (A), a resin having one or more structures selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. The component (A) exhibits flexibility by having one or more structures selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. As described above, even if the thermal conductivity can be improved by simply highly filling the component (C), the filling property is lowered and the peel strength is lowered. By containing a flexible resin such as the component (A), the affinity between the resin component and the components (C) and (F) is improved, or the adhesion as a whole is improved. It is possible to obtain an insulating layer having excellent peel strength while suppressing a decrease.

More specifically, the component (A) is one or two selected from a butadiene structure such as polybutadiene and hydrogenated polybutadiene, a polysiloxane structure such as silicone rubber, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure. It is preferable to have the above structure, and it is more preferable to have a polybutadiene structure.

The component (A) is preferably 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 9000, 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 may be usually −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) described later from the viewpoint of improving compatibility. The functional group that can react with the component (B) includes a functional group that appears 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, and a hydroxy group, an acid anhydride group, a phenolic hydroxyl group and an epoxy group are more preferable, and phenol. Phenol is particularly preferred. However, when an epoxy group is contained as a functional group, the component (A) does not have an aromatic structure.

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 less, and is 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 substance-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. 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 polybutadiene structure may be partially or wholly hydrogenated. Here, the "hydrogenated polybutadiene skeleton-containing resin" refers to 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.

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.

The number average molecular weight (Mn) of the butadiene resin is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, and more preferably 7,500 to 30 in order to exhibit flexibility and adhesion. It is 000, more preferably 10,000 to 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 in order to exhibit flexibility and adhesion. 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 group and carboxyl group introduced), "G-1000", "G-2000", "G-3000" (polybutadiene with double-ended hydroxyl group), "GI-1000", "GI-2000", "GI-3000" ( Both-terminal hydroxyl hydrogenated polybutadiene), "PB3600", "PB4700" (polybutadiene skeleton epoxy resin), "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (styrene, butadiene, and styrene block) manufactured by Daisel. Epoxides of copolymers), "FCA-061L" (hydrided polybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX Corporation, "R-45EPT" (polybutadiene skeleton epoxy resin), and the like.

Further, as another suitable embodiment of the component (A), a resin having one or more structures and an imide structure selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure is used. It can also be used. As such a component (A), a linear polyimide using hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials (polyimide described in JP-A-2006-37083, International Publication No. 2008/153208). And so on. The content of the polybutadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. For the 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.

Moreover, a preferable embodiment of the component (A) is a carbonate resin. The carbonate resin preferably has a glass transition temperature of 25 ° C. or lower, and is preferably 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, or an epoxy group-containing carbonate resin. One or more resins selected from the group consisting of isocyanate group-containing carbonate resins and urethane group-containing carbonate resins are preferred. 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) and functional group equivalent of the carbonate resin are the same as those of the butadiene resin, and the preferable ranges are 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 (PCT / JP2016 / 053609) 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, more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description of PCT / JP2016 / 053609 can be referred to, and the contents thereof are incorporated in the present specification.

Further, a preferred embodiment of the component (A) is a polysiloxane resin, an isoprene resin, or an isobutylene resin.

Specific examples of the polysiloxane resin include "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shinetsu Silicone Co., Ltd., an amine group-terminated polysiloxane, and a linear polyimide made from tetrabasic acid anhydride. International Publication No. 2010/053185) and the like can be mentioned. Specific examples of the isoprene resin include "KL-610" and "KL613" manufactured by Kuraray. Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutyrene block copolymer) manufactured by Kaneka Corporation.

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

<(B) Epoxy resin having an aromatic structure>
The resin composition of the present invention contains an epoxy resin having an aromatic structure as a component (B). The epoxy resin having an aromatic structure (hereinafter, may be simply referred to as “epoxy resin”) is not particularly limited as long as it has an aromatic structure. The aromatic structure is a chemical structure generally defined as an aromatic, and also includes a polycyclic aromatic and an aromatic heterocycle.

Examples of the epoxy resin having an aromatic structure 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 Tris. Phenol type epoxy resin, naphthol 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 with aromatic structure Resin, glycidyl ester type epoxy resin having an aromatic structure, 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, aromatic It has an alicyclic epoxy resin having a structure, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin having an aromatic structure, a cyclohexanedimethanol type epoxy resin having an aromatic structure, a naphthylene ether type epoxy resin, and an aromatic structure. Examples thereof include a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, and an aminophenol type epoxy resin. The epoxy resin may be used alone or in combination of two or more. 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 having an aromatic structure preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin having an aromatic structure is 100% by mass, it is preferable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule and having a liquid aromatic structure at a temperature of 20 ° C. (hereinafter referred to as “liquid epoxy resin”) and three or more epoxys in one molecule. It is preferable to contain an epoxy resin having a group and having a solid aromatic structure at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin having an aromatic structure, 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 novolak 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, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, aminophenol. Type epoxy resin is more preferred. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D" and "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, and "Selokiside 2021P" (having an ester skeleton) manufactured by Daicel. (Ali-ring type epoxy resin), “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd., and “YX7400” (high repulsion elastic epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. can be mentioned. These may be used alone or in combination of two or more.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin having an aromatic structure, 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, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthic are preferable. Lene ether type epoxy resin is more preferable, and naphthalene type tetrafunctional epoxy resin and 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" (naphthalen type tetrafunctional epoxy resin), and "N-690" manufactured by DIC. Cresol novolak type epoxy resin), "N-695" (cresol novolak 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 "(naphthol 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 Corporation. , "YL7760" (bisphenol AF type epoxy resin), "YX8800" (anthracene 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), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., "jER1031S" (tetraphenylethane type epoxy resin), "157S70" (bisphenol novolak 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 can be mentioned. These may be used alone or in combination of two or more.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (B), the amount ratio (solid epoxy resin: liquid epoxy resin) thereof 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) when used in the form of a resin sheet, appropriate adhesiveness is obtained, 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 having an aromatic structure in the resin composition is preferably 100% by mass 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 1% by mass or more, 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, still more preferably 6% by mass or less.

Further, the content of the epoxy resin having an aromatic structure in the resin composition is a resin composition excluding the component (C) and the component (F) from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. When the non-volatile component of the substance 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 having an aromatic structure 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 obtained. 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 having an aromatic structure 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) Thermally conductive filler>
The resin composition of the present invention contains (C) a thermally conductive filler, the average particle size of the component (C) is 2.5 μm to 5.0 μm, and the specific surface area is 0.8 m ² / g or more. .. By containing the component (C) having a predetermined average particle size and specific surface area, an insulating layer having excellent thermal conductivity and peel strength can be obtained. Further, since the component (C) having a predetermined average particle size and specific surface area has a high dispersibility, the filling property of the resin varnish can be improved. Here, in the present specification, the heat 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 it has a thermal conductivity within the above range, a predetermined average particle size and a predetermined specific surface area, and is not particularly limited, and is, for example, alumina, aluminum nitride, boron nitride, or carbide. Examples include silicon. 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 2.5 μm to 5.0 μm from the viewpoint of obtaining an insulating layer excellent in both thermal conductivity and peel strength and improving the filling property. The average particle size of the component (C) is preferably 2.5 μm to 4.8 μm, more preferably 2.5 μm to 4.5 μm. 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 using 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 0.8 m ² / g or more from the viewpoint of obtaining an insulating layer having excellent thermal conductivity and peel strength and improving the filling property. The specific surface area of the component (C) is preferably 0.8 m ² / g to 10 m ² / g, more preferably 0.8 m ² / g to 5 m ² / g. 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 Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The content of the component (C) is preferably 87% by mass or more, more preferably 87% by mass, 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) Curing agent>
The resin composition of the present invention may contain (D) a curing agent. The curing agent is not particularly limited as long as it has a function of curing the resin such as the component (B), and for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate ester. Examples thereof include a system curing agent and a carbodiimide system 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, an active ester-based curing agent, and a cyanate ester-based curing agent, and is preferably a phenol-based curing agent and an active ester-based curing agent. It is preferably one or more selected from the agents.

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-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-" "1163", "KA-1165", "GDP-6115L" manufactured by Gunei Chemical Co., Ltd., "GDP-6115H" and the like can be mentioned.

An active ester-based curing agent is also preferable from the viewpoint of obtaining an insulating layer having excellent adhesion to the metal layer. The active ester-based curing agent is not particularly limited, but generally contains an ester group having high reaction 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 esters is preferably used. The active ester-based 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-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, 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, fluoroglucin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compound, 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.

Commercially available products of active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. "65TM", "EXB-8000L-65TM" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, and "DC808" (manufactured by DIC) as an active ester compound containing an acetylated product of phenol novolac. Mitsubishi Chemical Co., Ltd.), "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester compound containing a benzoylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.) as an active ester-based curing agent which is an acetylated product of phenol novolac. Examples of the active ester-based curing agent which is a benzoyl compound of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) and the like.

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

Examples of the cyanate ester-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Echilidendiphenyl disyanate, 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 are phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan. Alternatively, a prepolymer in which the whole is triazined to become 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 (D), the content of the curing agent 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.

<(E) Curing accelerator>
The resin composition of the present invention may contain (E) 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 agents. A curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferable, and an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are more preferable. The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, 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. (5,4,0) -Undecene and the like are mentioned, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -Undecene are preferable.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 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 trimellitate, 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 Examples thereof include imidazole compounds such as 2-phenylimidazolin and adducts of the imidazole compound and an epoxy resin, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

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-octadecylviguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -Allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide and the like can be mentioned, with dicyandiamide and 1,5,7-triazabicyclo [4.4.0] deca-5-ene being preferred.

Examples of the metal-based curing accelerator include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include 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 an organic zinc complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex 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 (E), the content of the curing accelerator in the resin composition is not particularly limited, but 0.01% by mass when the non-volatile component in the resin composition is 100% by mass. ~ 1% by mass is preferable.

<(F) Inorganic filler (excluding those corresponding to (C) component)>
The resin composition of the present invention may contain (F) an inorganic filler. The material of the component (F) is not particularly limited, but for example, silica, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, hydroxylated. 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, zirconium oxide, barium titanate , Barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate 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, still more 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). Examples of commercially available inorganic fillers having such an average particle size include "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatex Co., Ltd., and "UFP-30" manufactured by Denki Kagaku Kogyo Co., Ltd. , Tokuyama "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 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, and titanate. It is preferable that the treatment is performed with one or more surface treatment agents such as a system coupling agent. The specific commercial products of the surface treatment agent are as described above.

When the resin composition contains the component (F), the content of the component (F) 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, still more 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.

<(G) Flame Retardant>
The resin composition may contain (G) a flame retardant. Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone-based 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 flame retardant 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. It is preferably 0.5% by mass to 5% by mass, more preferably 0.5% by mass to 3% by mass.

<(H) 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, defoaming agents, leveling agents, adhesion-imparting agents, and colorants can be mentioned.

<Physical characteristics of resin composition>
The cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 90 minutes exhibits a characteristic of being excellent in peel strength with a metal layer. Details show the characteristic that the peel strength between the cured product and the metal layer is excellent when the resin composition of the present invention is laminated on the metal layer and then heat-cured at 180 ° C. for 90 minutes. 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 copper foil> described later.
The metal layer is preferably a metal layer containing copper, and more preferably an electrolytic copper foil.

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. 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 resin composition of the present invention can provide an insulating layer having excellent thermal conductivity and peel strength, and since it contains the component (B), the compatibility of the component (A) is good. 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) for forming an insulating layer of a semiconductor chip package and a circuit board (including a printed wiring board). 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 resin composition for an interlayer insulating layer of a circuit board that forms a conductor layer).
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.

When the total mass of the high molecular weight component in the resin component contained in the resin composition is A and the total mass of the low molecular weight component is B, A / (A + B) preferably satisfies 0.15 or more, and is 0. It is more preferable to satisfy .20 or more, and further preferably to satisfy 0.25 or more. The lower limit is not particularly limited, but it is preferably satisfied with 0.60 or less, more preferably 0.55 or less, and further preferably 0.50 or less. Here, the high molecular weight component means a resin component contained in a resin composition having a weight average molecular weight of 10,000 or more, and a low molecular weight component means a resin component contained in a resin composition having a weight average molecular weight of 5,000 or less. To say. The method for measuring the weight average molecular weight is as described above.

[Resin sheet]
The resin sheet of the present invention comprises a support and a resin composition layer bonded to the support, and the resin composition layer comprises 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, and the like.

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

When a film made of a plastic material is used as a 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 polyimides. 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, aluminum foil, and the like, 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 support may be matted or corona-treated on the surface to be joined to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined to 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 mold release agent as a main component. Examples include "AL-5", "AL-7", "Lumilar T60" manufactured by Toray Industries, "Purex" manufactured by Teijin Ltd., and "Unipee" manufactured by Unitika Ltd.

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, and this resin varnish is applied onto a support using a die coater or the like and further dried to form a resin composition layer. It can be manufactured by.

Since the resin composition of the present invention contains (C) a thermally conductive filler, it can be applied onto a support or the like even if the solid content concentration of the resin varnish is 85% by mass or more, and it can be molded into a sheet shape. That is, it exhibits the property of being excellent in filling property. When the solid content concentration of the resin varnish is 85% by mass or more, the viscosity of the resin varnish is preferably 1.5 Pa · s or less, more preferably 1.3 Pa · s or less, still more preferably 1.0 Pa · s or less. Is. The lower limit is not particularly limited, but may be 0.01 Pa · s or more. The viscosity of the resin varnish is a value measured by an E-type viscometer at 25 ° C.

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 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. If the resin sheet has a protective film, it can be used by peeling off the protective film.

Instead of the resin sheet of the present invention, 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, and 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 may be in the same range as the resin composition layer in the above-mentioned resin sheet.

The resin sheet of the present invention 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 of the present invention 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 insulation in which a conductor layer is formed by plating on the resin sheet. It can be more preferably used for forming a layer (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 of the present invention 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). It can be suitably used for, for example, a Fan-out type WLP (Wafer Level Package), a Fan-in type WLP, a Fan-out type PLP (Panel Level Package), a Fan-in type PLP, or the like. Further, it can also be suitably used as a MUF (Molding Under Filling) material or the like used after connecting a semiconductor chip to a substrate.
The resin sheet of the present invention can also be suitably used for a wide range of other applications where high insulation reliability is required, for example, for forming an insulating layer of a circuit board such as a printed wiring board.

[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 the circuit board of the present invention is as follows.
(1) A step of preparing a base material with a wiring layer having a base material and a wiring layer as a metal 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 so that the wiring layer is embedded in the resin composition layer, and thermally curing the resin sheet to form an insulating layer.
(3) Includes a step of connecting the 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 a wiring layer different from the wiring layer as the metal layer can be interconnected, but is a step of forming a via hole in the insulating layer to form the wiring layer and polishing the insulating layer. Alternatively, it is preferably at least one of the steps of grinding and exposing the wiring layer.

<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, respectively, and is on the side opposite to the surface of the second metal layer on the base material side. It has a wiring layer on the surface. For details, a dry film (photosensitive resist film) is laminated on a substrate 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, even if 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 manufactured by Mitsui Mining & Smelting Co., Ltd., trade name "Micro Tin") is formed on the surface. good.

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 photoresist 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, cost, ease of patterning, etc. for forming the wiring layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. A nickel alloy, a copper-titanium alloy alloy layer is preferable, a chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer, or a nickel-chromium alloy alloy layer is more preferable, and a copper single metal layer is 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 μm. When the step of polishing or grinding the insulating layer in step (3) to expose the wiring layer and interconnecting the wiring layer different from the wiring layer as the metal layer is adopted, the wiring is not connected to the wiring to be interconnected. It is preferable that the thickness of the wiring is 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 design of the desired wiring board, but is preferably 100 μm or less and 2 μm or more. 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)>
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 thermally curing the resin sheet to form an insulating layer. For details, the wiring layer of the base material with a 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 thermally cured and insulated. Form a layer.

The laminating of the wiring layer and the resin sheet can be performed, for example, by 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-crimping the resin sheet to the wiring layer (hereinafter, also referred to as “heat-crimping 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 with a pressure of 13 hPa or less.

After laminating, the laminated resin sheet may be smoothed by pressing under normal pressure (under atmospheric pressure), for example, from the support side. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The laminating 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 thermally cured to form an insulating layer. For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition 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. Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature.

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

<Process (3)>
The step (3) is a step of connecting the wiring layers to each other. The details are a step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers to each other. Alternatively, it is a step of polishing or grinding the insulating layer to expose the wiring layer and connecting the wiring layer different from the metal 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 examples thereof include laser irradiation, etching, and mechanical drilling. 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 and exposes 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 the plating step, the via hole may be subjected to, for example, a wet desmear treatment, and when the conductor layer is formed by the sputtering step, for example, a plasma treatment step may be performed. A dry plasma 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 dry roughening treatment include plasma treatment, and examples of wet roughening treatment include swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. Can be mentioned.

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 thin film deposition, and is preferably formed by plating. In one preferred embodiment, the surface of the insulating layer can be plated by 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. Further, when the support in the resin sheet is a metal leaf, 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.

For details, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. 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 a step of polishing or grinding the insulating layer to expose the wiring layer as the metal layer and connecting the wiring layer different from the metal layer to each other is adopted, the method of polishing or grinding the insulating layer is to use the wiring layer. It is not particularly limited as long as it can be exposed and the polishing or grinding surface is horizontal, and a conventionally known polishing method or grinding method can be applied. Examples include a mechanical polishing method and a surface grinding method by rotating a grindstone. Similar to the step of forming a via hole in the insulating layer, forming the conductor layer, and connecting the wiring layers to each other, a smear removing step and a roughening treatment step may be performed, or the conductor layer may be formed. Further, it is not necessary to expose all the wiring layers as metal layers, and a part of the wiring layers as metal layers may be exposed.

<Process (4)>
The 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 substrate may be peeled off with the conductor layer protected by a protective film.

[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 of the present invention. A semiconductor chip package can be manufactured by joining a semiconductor chip to the circuit board of the present invention.

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 via an insulating adhesive.

A preferred embodiment is to crimp a semiconductor chip to a 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).

In addition, another preferred embodiment reflows and joins a semiconductor chip to a circuit board. The reflow condition can be, for example, in the range of 120 ° C to 300 ° C.

After joining the semiconductor chip to the circuit board, for example, the semiconductor chip can be filled with a mold underfill material to obtain a semiconductor chip package. 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 a bump 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 have been 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; copper, titanium, stainless steel, metal substrate such as cold rolled steel plate (SPCC); glass fiber impregnated with epoxy resin or the like and heat-cured (for example, FR-). 4 Substrate); Examples thereof include a substrate made of bismaleimide triazine resin (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 by 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 production number of the target semiconductor package, 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 the semiconductor chip or applying the resin composition of the present invention on the semiconductor chip and thermosetting to form a sealing layer. be. In the step (C), it is preferable that the resin composition layer of the resin sheet of the present invention is laminated on the semiconductor chip and thermally cured to form a sealing layer.

The semiconductor chip and the resin sheet can be laminated 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-crimping the resin sheet to the semiconductor chip (hereinafter, also referred to as “heat-crimping 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 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 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. Further, in the method of irradiating the substrate side with ultraviolet rays to reduce the adhesive force of the temporary fixing film and peeling it off, the irradiation amount of the ultraviolet rays is usually 10 mJ / cm ² to 1000 mJ / 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 of the semiconductor chip and the temporary fixing film 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, the material is not particularly limited. 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 the material for forming the rewiring cambium (insulating layer) is a photosensitive resin in forming the via hole, first, the surface of the rewiring cambium (insulating layer) is irradiated with active energy rays through a mask pattern and irradiated. The most wiring layer of the part is photo-cured.

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 method includes a contact exposure method in which the mask pattern is exposed in close contact with the rewiring cambium (insulating layer) and an exposure method using parallel light rays without the mask pattern in 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 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 may 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)>
The 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 a 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 is, 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. 1 as an example. 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 "%" 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) Preparation of resin sheet PET film ("Lumilar R80" manufactured by Toray Industries, Inc.) obtained by mold-releasing the resin varnish prepared in Examples and Comparative Examples with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Co., Ltd.). A thickness of 38 μm, a softening point of 130 ° C., hereinafter sometimes referred to as “release PET”) is applied with a die coater so that the thickness of the resin composition layer after drying is 100 μm, and the thickness is 80 ° C. to 100. A resin sheet was obtained by drying at ° C. (average 90 ° C.) for 7 minutes.

(3) Laminating of resin sheet The resin composition layer is bonded to the inner layer circuit board by using a batch type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.). As described above, they were laminated on both sides of 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 120 ° C. and a pressure of 0.74 MPa for 30 seconds. Then, heat pressing was performed at 120 ° C. and a pressure of 0.5 MPa for 60 seconds.

(4) Laminating with a metal layer (copper foil) After that, the support is peeled off, and electrolysis is performed so that the resin composition layer and the roughened surface of the electrolytic copper foil are bonded to the surface of the exposed resin composition layer. Copper foil (“JTCP” manufactured by JX Nikko Nisseki Metal Co., Ltd., thickness 35 μm, maximum height of roughened surface (Rz: JIS B0601-2001): 6 μm) was laminated. Then, using the above-mentioned laminator device, stacking was performed under the same conditions.

(5) Curing of Resin Composition After laminating, the resin composition layer was cured under the curing conditions of 180 ° C. for 90 minutes.

<Measurement and evaluation of peeling strength (peeling strength) of copper foil>
Make a notch in the electrolytic copper foil with a width of 10 mm and a length of 100 mm, peel off one end of the cut, and grab it with a gripping tool (autocom type testing machine "AC-50C-SL" manufactured by TSE). At room temperature, the load (kgf / cm) when 20 mm was peeled off in the vertical direction at a speed of 50 mm / min was measured, and the peel strength was determined.

<Measurement of thermal conductivity of cured product>
(1) Preparation of cured product sample PET film ("Lumilar R80" manufactured by Toray Co., Ltd.) obtained by mold-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., hereinafter sometimes referred to as “release PET”), and applied with a die coater so that the thickness of the resin composition layer after drying is 100 μm, from 80 ° C. A resin sheet was obtained by drying at 100 ° C. (average 90 ° C.) for 7 minutes.

The prepared resin sheet was laminated with three resin composition layers using a batch type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.), and then 180 ° C. for 90 minutes. The resin composition layer was cured under the curing conditions to obtain a sample. The laminate was depressurized for 30 seconds to a pressure of 13 hPa or less, and then pressed at 120 ° C. and a pressure of 0.4 MPa for 20 seconds to obtain a cured product sample.

(2) Measurement of heat diffusion rate α For the cured product sample, the heat diffusion rate 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 The 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 Metler Toledo.

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

<Evaluation of filling property>
A resin varnish was prepared so that the solid content concentration of the resin varnish produced in Examples and Comparative Examples was 85% by mass or more, and a mold release treatment was performed with an alkyd resin-based mold release agent (“AL-5” manufactured by Lintec Co., Ltd.). On a PET film (“Lumilar R80” manufactured by Toray Co., Ltd., thickness 38 μm, softening point 130 ° C., hereinafter sometimes referred to as “release PET”), the thickness of the resin composition layer after drying is 100 μm. It was applied with a die coater. ○ when it was possible to mold into a sheet without any problem, △ when the viscosity of the resin varnish exceeded 1.5 Pa · s (25 ° C, E-type viscometer), and the formability was poor and there were streaks, the viscosity of the resin varnish Was more than 2.5 Pa · s (25 ° C., E-type viscometer), and the case where the sheet could not be formed was marked with x.

<Synthesis Example 1: Synthesis of Elastomer 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 Ipsol 150 in a reaction vessel. (Aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical 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 while further stirring, and the reaction was carried out for about 3 hours. Next, the reaction product was 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 ethyl diglycol acetate (manufactured by Daicel) were added thereto. Then, 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 100-mesh filter cloth to obtain an elastomer 1 (nonvolatile content 50% by mass) having a polybutadiene structure and a phenolic hydroxyl group. rice field. The number average molecular weight was 5500.

<Synthesis Example 2: Synthesis of Elastomer 2>
50 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 Ipsol 150 in a reaction vessel. (Aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) 23.5 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 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) Was added while further stirring, and the reaction was carried out for about 3 hours. Then, the reaction product is cooled to room temperature, and then 8.96 g of benzophenone tetracarboxylic acid dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, and ethyldiglycol are added to the reaction product. 40.4 g of acetate (manufactured by Daicel) 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, the reaction product is cooled to room temperature, filtered through a 100-mesh filter cloth, and elastomer 2 having an imide structure, a urethane structure, and a polybutadiene structure (nonvolatile content: 50% by mass). ) Was obtained. The number average molecular weight was 13700.

<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.).

<The heat conductive filler used>
Alumina 1: Alumina having different average particle diameter and specific surface area was mixed and prepared so as to have an average particle size of 4.2 μm and a specific surface area of 0.8 m ² / g.
Alumina 2: Alumina having different average particle diameter and specific surface area was mixed and prepared so as to have an average particle size of 3.0 μm and a specific surface area of 1.5 m ² / g.
Alumina 3: Alumina with an average particle diameter of 4 μm (“CB-P05” manufactured by Showa Denko KK, specific surface area 0.7 m ² / g)
Alumina 4: Alumina with an average particle diameter of 2 μm (“CB-P02” manufactured by Showa Denko KK, specific surface area 1.1 m ² / g)

<Example 1>
High resilience elastic epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 440 g / eq) 4 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) 3 parts, bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent: 185 g / eq) 2 parts dissolved in 10 parts of cyclohexanone. 215 parts of alumina 1, 20 parts of elastomer 1 (solid content 50% by mass, number average molecular weight 5500), solid naphthol-based curing agent ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl group equivalent 215, solid content 50% MEK solution ) 6 parts, curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) and 15 parts of methyl ethyl ketone are mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. bottom.

<Example 2>
High resilience elastic epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 440 g / 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) 2 parts, bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent: 185 g / eq) 2 parts dissolved in 10 parts of cyclohexanone. 210 parts of alumina 2, 20 parts of elastomer 1 (solid content 50% by mass, number average molecular weight 5500), solid naphthol-based curing agent ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl group equivalent 215, solid content 50% MEK solution ) 6 parts, curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) and 15 parts of methyl ethyl ketone are mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. bottom.

<Example 3>
High resilience elastic epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 440 g / eq) 4 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) 4 parts, bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent: 185 g / eq) 2 parts dissolved in 10 parts of cyclohexanone. 210 parts of alumina 2, 24 parts of elastomer 1 (solid content 50% by mass, number average molecular weight 5500), solid naphthol-based curing agent ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl group equivalent 215, solid content 50% MEK solution ) 6 parts, curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) and 13 parts of methyl ethyl ketone are mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. bottom.

<Example 4>
High resilience elastic epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 440 g / eq) 4 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) 4 parts, bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent: 185 g / eq) 2 parts dissolved in 7 parts of cyclohexanone. 170 parts of alumina 2, 24 parts of elastomer 1 (solid content 50% by mass, number average molecular weight 5500), solid naphthol-based curing agent ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl group equivalent 215, solid content 50% MEK solution ) 6 parts, a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) and 9 parts are mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. bottom.

<Example 5>
High resilience elastic epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 440 g / eq) 4 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) 4 parts, bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent: 185 g / eq) 3 parts dissolved in cyclohexanone 13 parts. 215 parts of alumina 1, 12 parts of elastomer 1 (solid content 50% by mass, number average molecular weight 5500), solid naphthol-based curing agent ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl group equivalent 215, solid content 50% MEK solution ) 8 parts, a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) and 15 parts are mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. bottom.

<Example 6>
High resilience elastic epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 440 g / eq) 4 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) 3 parts, bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent: 185 g / eq) 2 parts dissolved in 10 parts of cyclohexanone. 215 parts of alumina 1, 20 parts of elastomer 2 (solid content 50% by mass, number average molecular weight 13700), solid naphthol-based curing agent ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl group equivalent 215, solid content 50% MEK solution ) 6 parts, curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) and 15 parts of methyl ethyl ketone are mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. bottom.

<Example 7>
High resilience elastic epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 440 g / eq) 4 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) 4 parts, bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent: 185 g / eq) 2 parts dissolved in 10 parts of cyclohexanone. 210 parts of alumina 2, 24 parts of elastomer 2 (solid content 50% by mass, number average molecular weight 13700), solid naphthol-based curing agent (“SN485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl group equivalent 215, solid content 50% MEK solution ) 6 parts, curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) and 13 parts of methyl ethyl ketone are mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. bottom.

<Comparative Example 1>
High resilience elastic epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 440 g / eq) 4 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, bixirenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent: 185 g / eq) 3 parts dissolved in 14 parts of cyclohexanone. 215 parts of alumina 1, 5 parts of polyester resin (UE3400 manufactured by Unitika), 10 parts of solid naphthol-based curing agent ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution with 50% solid content), curing An accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) and 18 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

<Comparative Example 2>
High resilience elastic epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 440 g / eq) 4 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, bixirenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent: 185 g / eq) 3 parts dissolved in 5 parts of cyclohexanone. 100 parts of alumina 1, 5 parts of polyester resin (UE3400 manufactured by Unitika), 10 parts of solid naphthol-based curing agent ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution with 50% solid content), curing An accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) and 7 parts of methyl ethyl ketone were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

<Comparative Example 3>
High resilience elastic epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 440 g / eq) 4 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) 3 parts, bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent: 185 g / eq) 2 parts dissolved in 10 parts of cyclohexanone. MEK solution containing 215 parts of alumina 3, 20 parts of elastomer 1 (solid content 50% by mass, number average molecular weight 5500), solid naphthol-based curing agent ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl group equivalent 215, solid content 50%). ) 6 parts, curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) and 15 parts of methyl ethyl ketone are mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. bottom.

<Comparative Example 4>
High resilience elastic epoxy resin ("YX7400" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 440 g / eq) 4 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) 4 parts, bixylenol type epoxy resin (Mitsubishi Chemical Co., Ltd. "YX4000HK", epoxy equivalent: 185 g / eq) 2 parts dissolved in 10 parts of cyclohexanone. 210 parts of alumina 4, 24 parts of elastomer 1 (solid content 50% by mass, number average molecular weight 5500), solid naphthol-based curing agent ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., hydroxyl group equivalent 215, solid content 50% MEK solution ) 6 parts, curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass) and 13 parts of methyl ethyl ketone are mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. bottom.

The abbreviations in the table below are as follows.
Elastomer 1: Elastomer Elastomer manufactured in Synthesis Example 2: Epoxy YX7400 manufactured in Synthesis Example 2: High repulsion elastic epoxy resin, epoxy equivalent 440 g / eq, ZX1059 manufactured by Mitsubishi Chemical Corporation: Bisphenol A type epoxy resin and Bisphenol F type epoxy 1: 1 mixture with resin (mass ratio), epoxy equivalent: 169 g / eq, Nittetsu Sumikin Chemical Co., Ltd. YX4000HK: Bisphenol type epoxy resin, epoxy equivalent, 185 g / eq, Mitsubishi Chemical Co., Ltd. alumina 1: average particle size And a mixture of alumina with different specific surface areas, average particle size 4.2 μm, specific area area 0.8 m ² / g
Alumina 2: A mixture of alumina with different average particle size and specific surface area, average particle size 3.0 μm, specific surface area 1.5 m ² / g
Alumina 3: Alumina with an average particle diameter of 4 μm (“CB-P05” manufactured by Showa Denko KK, specific surface area 0.7 m ² / g)
Alumina 4: Alumina with an average particle diameter of 2 μm (“CB-P02” manufactured by Showa Denko KK, specific surface area 1.1 m ² / g)
SN485: Solid naphthol-based curing agent, hydroxyl group equivalent 215, MEK solution with solid content of 50%, DMAP manufactured by Nippon Steel & Sumitomo Metal Corporation: Curing accelerator, 4-dimethylaminopyridine, MEK solution with solid content of 5% by mass UE3400: Polyester resin , Content of component (A) manufactured by Unitika: Indicates the content (% by mass) when the non-volatile component of the resin composition excluding the component (C) is 100% by mass.
Content of component (C): Represents the content (% by mass) when the non-volatile component of the resin composition is 100% by mass.

As shown in Examples 1 to 7, it can be seen that the insulating layer formed from the resin composition containing the components (A) to (C) is excellent in thermal conductivity and peel strength with respect to the metal layer. Further, it can be seen that since Examples 1 to 7 are excellent in filling property, it is easy to form a film in the form of a sheet. On the other hand, it can be seen that the peel strengths of Comparative Examples 1 and 2 containing no component (A) are inferior to those of Examples 1 to 7. Further, in Comparative Examples 3 to 4 containing no component (C), since the viscosity exceeded 2.5 Pa · s, they could not be molded into a sheet shape, and the peel strength and thermal conductivity could be evaluated. There wasn't. It has been confirmed that even when the components (D) and (E) are not contained, the same results as those in the above-mentioned Examples are obtained, 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 (14)

(A) The number average molecular weight (Mn) is 1,000 to 1,000,000, and one or more selected from resins having a glass transition temperature of 25 ° C. or lower and resins that are liquid at 25 ° C. A resin,
It contains (B) an epoxy resin having an aromatic structure and (C) a thermally conductive filler.
The average particle size of the component (C) is 2.5 μm to 5.0 μm, and the specific surface area is 0.8 m ² / g or more .
The component (A) has a polybutadiene structure and has a polybutadiene structure.
The component (A) is a resin composition having one or more functional groups 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 . .. The resin composition according to claim 1, wherein the peel strength between the cured product obtained by thermally curing the resin composition at 180 ° C. for 90 minutes and the metal layer is 0.4 kgf / cm or more. The resin composition according to claim 1 or 2, wherein the cured product obtained by thermally curing the resin composition at 180 ° C. for 90 minutes and the electrolytic copper foil have a peel strength of 0.4 kgf / cm or more. The resin composition according to any one of claims 1 to 3, wherein the content of the component (C) is 87% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 4, wherein the component (C) is alumina. According to any one of claims 1 to 5, 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 to 5.0 W / m · K. The resin composition described. 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 resin composition according to any one of claims 1 to 7 , wherein the component (A) has an imide structure. The resin composition according to any one of claims 1 to 8 , which is a resin composition for an insulating layer of a semiconductor chip package. 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 claims 1 to 9 . The resin sheet according to claim 10, which is a resin sheet for an insulating layer of a semiconductor chip package. A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 9 . A semiconductor chip package including the circuit board according to claim 12 and a semiconductor chip mounted on the circuit board. A semiconductor chip package comprising a semiconductor chip sealed with the resin composition according to any one of claims 1 to 9 or the resin sheet according to claim 10 or 11.

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