KR102400207B1 - Resin composition - Google Patents

Abstract

[Problem] Provision of a resin composition capable of obtaining an insulating layer having excellent thermal diffusivity and adhesion strength to a metal layer, a resin sheet, a circuit board, and a semiconductor chip package using the resin composition.
[Solution means] (A) a resin having at least one structure selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule, (B) an epoxy resin having an aromatic structure and (C) a thermally conductive filler, wherein the component (C) has an average particle diameter of 2.5 µm to 5.0 µm and a specific surface area of 0.8 m 2 /g or more.

Description

Resin composition {RESIN COMPOSITION}

The present invention relates to a resin composition. Moreover, it is related with the resin sheet, the circuit board, and the semiconductor chip package which used the resin composition.

In recent years, miniaturization and high functionalization of electronic devices progress, and there exists a tendency for the mounting density of the semiconductor element in a printed wiring board to become high. In addition to the high functionality of the semiconductor device to be mounted, a technique for efficiently diffusing the heat generated by the semiconductor device is required.

For example, in patent document 1, spreading|diffusion of heat is disclosed by using for a printed wiring board the insulating layer which hardened|cured resin and the high thermal conductivity resin composition containing the inorganic filler which has a specific average particle diameter.

Japanese Patent Laid-Open No. 2013-189625

The present inventors examined the thermal conductivity of an insulating layer in order to diffuse the heat which a semiconductor element generate|occur|produces more efficiently. As a result, the inventors found that when an insulating layer is formed by curing a resin composition containing a thermally conductive filler, the thermal conductivity of the obtained insulating layer has a trade-off relationship with the adhesion strength (peel strength) to the metal layer. did. Specifically, by increasing the content of the thermally conductive filler in the resin composition, the thermal conductivity of the obtained insulating layer can be improved, but if the content of the thermally conductive filler is increased to an extent to express sufficient thermal conductivity, the obtained insulating layer is It was found that the adhesion strength was lowered.

The present invention, a resin composition capable of obtaining an insulating layer excellent in thermal conductivity and adhesion strength to the metal layer; It is providing the resin sheet, circuit board, and semiconductor chip package which used the said resin composition.

The present inventors, (A) a resin having at least one structure selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule, (B) an epoxy resin having an aromatic structure , and (C) by containing a thermally conductive filler having a predetermined average particle diameter and a predetermined specific surface area, it was discovered that an insulating layer excellent in thermal conductivity and adhesion strength to a metal layer can be obtained, and the present invention has been completed.

That is, the present invention includes the following contents.

[1] (A) a resin having in its molecule at least one structure selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure;

(B) an epoxy resin having an aromatic structure, and

(C) contains a thermally conductive filler,

(C) The average particle diameter of component is 2.5 micrometers - 5.0 micrometers, The resin composition whose specific surface area is 0.8 m<2>/g or more.

[2] The resin composition according to [1], wherein the cured product obtained by thermosetting the resin composition at 180° C. for 90 minutes and the metal layer have a peel strength of 0.4 kgf/cm or more.

[3] The resin composition according to [1] or [2], wherein the cured product obtained by thermosetting 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 nonvolatile 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] The resin composition according to any one of [1] to [5], wherein a cured product obtained by thermosetting the resin composition at 180°C for 90 minutes has a thermal conductivity of 1.5 W/m·K to 5.0 W/m·K.

[7] The resin 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 less and a resin liquefied at 25°C.

[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] The resin according to any one of [1] to [8], wherein the component (A) has at least one functional group selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. composition.

[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 has 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 having a support and a resin composition layer formed on the support and comprising 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 comprising 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 comprising the circuit board according to [16] and a semiconductor chip mounted on the circuit board.

[18] A semiconductor chip package comprising a semiconductor chip sealed with the resin composition according to any one of [1] to [13] or the resin sheet according to [14] or [15].

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

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

EMBODIMENT OF THE INVENTION Hereinafter, the resin composition of this invention, a resin sheet, a circuit board, and a semiconductor chip package are demonstrated in detail.

[resin composition]

The resin composition of the present invention comprises (A) a resin having at least one structure selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule, (B) an aromatic structure It contains the epoxy resin which has, and (C) a thermally conductive filler, (C) component average particle diameter is 2.5 micrometers - 5.0 micrometers, and a specific surface area is 0.8 m<2>/g or more.

By containing component (A), component (B), and component (C) having a predetermined average particle diameter and a predetermined specific surface area in the resin composition, it is possible to obtain an insulating layer excellent in thermal conductivity and peel strength to the metal layer becomes The resin composition may further contain (D) a curing agent, (E) a curing accelerator, (F) an inorganic filler (excluding those corresponding to component (C)) and (G) a flame retardant, if necessary. Hereinafter, each component contained in a resin composition is demonstrated in detail.

<(A) Resin having at least one structure selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule>

The resin composition of the present invention contains, as component (A), a resin having at least one structure selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule. (A) component shows flexibility by having 1 or more types of structures chosen from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule|numerator. As above-mentioned, only by high filling of (C)component, even if thermal conductivity can be improved, while filling property falls, peeling strength falls. By containing flexible resin like component (A), the affinity of a resin component and (C)component and (F)component improves, or the fall of fillability is suppressed by the reason that adhesiveness improves as a whole, and peeling strength can obtain an excellent insulating layer.

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

(A) In order to show a softness|flexibility, it is preferable that it is high molecular weight, and a number average molecular weight (Mn) becomes like this. Preferably it is 1,000-1,000,000, More preferably, it is 5,000-900,000. A number average molecular weight (Mn) is a polystyrene conversion number average molecular weight measured using GPC (gel permeation chromatography).

In order that component (A) shows flexibility, at least 1 type of resin selected from the resin whose glass transition temperature (Tg) is 25 degrees C or less, and the resin which is liquid at 25 degreeC is preferable.

The glass transition temperature of resin whose glass transition temperature (Tg) is 25 degrees C or less becomes like this. Preferably it is 20 degrees C or less, More preferably, it is 15 degrees C or less. Although the lower limit of a glass transition temperature is not specifically limited, Usually, it can be made into -15 degreeC or more. Moreover, as resin which is liquid at 25 degreeC, Preferably it is resin which is liquid at 20 degrees C or less, More preferably, it is resin which is liquid at 15 degrees C or less.

As (A) component, it is preferable to have a functional group which can react with (B) component mentioned later from a viewpoint of improving compatibility. In addition, as a functional group which can react with (B) component, the functional group shown by heating shall be included.

In one suitable embodiment, the functional group capable of reacting with component (B) is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. . Among these, the functional group is preferably a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group, more preferably a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, or an epoxy group, and a phenolic hydroxyl group Especially preferred. However, when an epoxy group is included as a functional group, (A) component does not have an aromatic structure.

One suitable embodiment of component (A) is a butadiene resin. As the butadiene resin, a butadiene resin having a liquid phase or glass transition temperature of 25°C or lower at 25°C is preferable, and a hydrogenated polybutadiene skeleton-containing resin, a hydroxyl group-containing butadiene resin, a phenolic hydroxyl group-containing butadiene resin, a carboxyl group-containing butadiene resin, and an acid anhydride At least one resin selected from the group consisting of a group-containing butadiene resin, an epoxy group-containing butadiene resin, an isocyanate group-containing butadiene resin and a urethane group-containing butadiene resin is more preferable, and a phenolic hydroxyl group-containing butadiene resin is still more preferable. Here, the "butadiene resin" refers to resin containing a polybutadiene structure, and in these resins, the polybutadiene structure may be contained in the main chain or may be contained in the side chain. The polybutadiene structure may be partially or entirely hydrogenated. Here, "hydrogenated polybutadiene skeleton-containing resin" means resin in which at least a part of polybutadiene skeleton is hydrogenated, and it is not necessarily resin in which polybutadiene skeleton was completely hydrogenated.

As hydrogenated polybutadiene skeleton containing resin, hydrogenated polybutadiene skeleton containing epoxy resin etc. are mentioned, for example. As phenolic hydroxyl group containing butadiene resin, resin etc. which have a polybutadiene structure and have a phenolic hydroxyl group are mentioned, for example.

The number average molecular weight (Mn) of the butadiene resin is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, more preferably 7,500 to 30,000, still more preferably 10,000 to 15,000 in order to exhibit flexibility and adhesiveness. . Here, the number average molecular weight (Mn) of resin is a polystyrene conversion number average molecular weight measured 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 show flexibility and adhesiveness. In addition, a functional group equivalent is the number of grams of resin containing the functional group of 1 gram equivalent. For example, an epoxy group equivalent can be measured according to JISK7236. The hydroxyl 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) manufactured by Clay Valley, "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", "Ricon 131MA17" , "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing an acid anhydride group), "JP-100", "JP-200" (epoxidized polybutadiene) manufactured by Nippon Soda, "GQ-1000" (hydroxyl group) , carboxyl group-introduced polybutadiene), “G-1000”, “G-2000”, “G-3000” (polybutadiene with hydroxyl groups at both ends), “GI-1000”, “GI-2000”, “GI-3000” ( Polybutadiene hydrogenated at both terminals), "PB3600", "PB4700" (polybutadiene skeleton epoxy resin) manufactured by Daicel, "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (styrene, butadiene and styrene) The epoxidized product of a block copolymer), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin) by Nagase Chemtex, "R-45EPT" (polybutadiene skeleton epoxy resin), etc. are mentioned.

In addition, as another suitable embodiment of the component (A), a resin having at least one structure selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure and an imide structure is used. may be As the component (A), a linear polyimide using a hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials (a polyimide described in Japanese Patent Application Laid-Open No. 2006-37083 and International Publication No. 2008/153208) mid) and the like. The content rate of the polybutadiene structure of the said polyimide resin becomes like this. Preferably it is 60 mass % - 95 mass %, More preferably, it is 75 mass % - 85 mass %. For the detail of the said polyimide resin, description of Unexamined-Japanese-Patent No. 2006-37083 and International Publication No. 2008/153208 can be considered into consideration, and the content is taken in here.

In addition, one preferred embodiment of the component (A) is a carbonate resin. As the carbonate resin, a carbonate resin having a glass transition temperature of 25° C. or less is preferable, a hydroxyl group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxyl group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an epoxy group-containing carbonate resin, and an isocyanate group-containing At least one resin selected from the group consisting of a carbonate resin and a carbonate resin containing a urethane group is preferable. Here, "carbonate resin" refers to resin containing a polycarbonate structure, and in these resins, the polycarbonate structure may be contained in the main chain or may be contained in the side chain.

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

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

In addition, it is also possible to use a linear polyimide (International Publication No. 2016/129541 (PCT/JP2016/053609)) using a hydroxyl-terminated polycarbonate, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials. The content rate of the polycarbonate structure of the said polyimide resin becomes like this. Preferably it is 60 mass % - 95 mass %, More preferably, it is 75 mass % - 85 mass %. For details of the polyimide resin, reference can be made to the description of International Publication No. 2016/129541 (PCT/JP2016/053609), the content of which is incorporated herein by reference.

Moreover, one suitable embodiment of additional (A) component is a polysiloxane resin, an isoprene resin, and isobutylene resin.

As a specific example of polysiloxane resin, "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., an amine group-terminated polysiloxane, and a linear polyimide using a tetrabasic acid anhydride as raw materials (International Publication No. 2010/ 053185) and the like. As a specific example of an isoprene resin, "KL-610", "KL613" by Kuraray Corporation, etc. are mentioned. Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation. there is.

The content of component (A) in the resin composition, from the viewpoint of imparting flexibility, when the nonvolatile component of the resin composition excluding component (C) and component (F) is 100% by mass, preferably 65% by mass or less, More preferably, it is 60 mass % or less, More preferably, it is 55 mass % or less, More preferably, it is 50 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 this invention contains the epoxy resin which has an aromatic structure as (B) component. The epoxy resin (hereinafter, simply referred to as "epoxy resin" in some cases) having an aromatic structure will not be particularly limited as long as it has an aromatic structure. An aromatic structure is a chemical structure generally defined as aromatic, and polycyclic aromatic and aromatic heterocyclic ring are also included.

Examples of the epoxy resin having an aromatic structure include a bixylenol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, Trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycy having an aromatic structure Diylamine type epoxy resin, glycidyl ester type epoxy resin with aromatic structure, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin with aromatic structure, epoxy resin with butadiene structure with aromatic structure , an alicyclic epoxy resin having an aromatic 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, a trimethylol type having an aromatic structure An epoxy resin, a tetraphenylethane type|mold epoxy resin, an aminophenol type epoxy resin, etc. are mentioned. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. It is preferable that (B) component is 1 or more types chosen from a bisphenol A epoxy resin, a bisphenol F type epoxy resin, an aminophenol type epoxy resin, and a naphthalene type epoxy resin.

It is preferable that the epoxy resin which has an aromatic structure contains the epoxy resin which has two or more epoxy groups in 1 molecule. When the nonvolatile component of the epoxy resin which has an aromatic structure is 100 mass %, it is preferable that at least 50 mass % or more is an epoxy resin which has two or more epoxy groups in 1 molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule and having an aromatic structure that is liquid at a temperature of 20°C (hereinafter referred to as “liquid epoxy resin”), and three or more epoxy groups in one molecule, having a temperature of 20 It is preferable to contain the epoxy resin (henceforth "solid-state epoxy resin") which has an aromatic structure which is solid at degreeC. As an epoxy resin having an aromatic structure, a resin composition having excellent flexibility is obtained by using a liquid epoxy resin and a solid epoxy resin together. Moreover, the breaking strength of the hardened|cured material of a resin composition also improves.

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 aromatic structure. Resin, a phenol novolak type epoxy resin, an alicyclic epoxy resin having an ester skeleton having an aromatic structure, a cyclohexanedimethanol type epoxy resin having an aromatic structure, an aminophenol type epoxy resin, and an epoxy resin having a butadiene structure having an aromatic structure is preferable, and bisphenol A epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, aminophenol type epoxy resin, and naphthalene type epoxy resin are more preferable, bisphenol A type epoxy resin, bisphenol F type epoxy resin, amino A phenol-type epoxy resin is more preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, "828US" manufactured by Mitsubishi Chemical Corporation, "jER828EL" (bisphenol A type epoxy resin), " jER806", "jER807" (bisphenol F-type epoxy resin), "jER152" (phenol novolak-type epoxy resin), "630", "630LSD" (glycidylamine-type epoxy resin), manufactured by Shin-Nittetsu Sumikin Chemical "ZX1059" (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) of ' (alicyclic epoxy resin having an ester skeleton), "ZX1658", "ZX1658GS" (liquid 1,4-glycidyl cyclohexane) manufactured by Nippon Chemicals Co., Ltd. (Liquid 1,4-glycidylcyclohexane), "YX7400" manufactured by Mitsubishi Chemical Corporation (high repulsion elasticity) epoxy resin). These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid-state epoxy resin include a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin having an aromatic structure, a trisphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, and naphthylene. Ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin , a naphthylene ether type epoxy resin is more preferable, and a naphthalene type tetrafunctional epoxy resin and a naphthylene ether type epoxy resin are still more preferable. As a specific example of a solid epoxy resin, "HP4032H" (naphthalene type epoxy resin) manufactured by DIC, "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac) type epoxy resin), “N-695” (cresol novolak type epoxy resin), “HP-7200”, “HP-7200L”, “HP-7200HH”, “HP-7200H”, “HP-7200HHH” (D Cyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-" manufactured by Nippon Kayaku 502H" (trisphenol-type epoxy resin), "NC7000L" (naphthol novolac-type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl-type epoxy resin), New Nittetsu Sumikin Kaga "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolak type epoxy resin) manufactured by KUSA, "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin), "YX4000HK" (Vek) Silenol-type epoxy resin), "YL7760" (bisphenol AF-type epoxy resin), "YX8800" (anthracene-type epoxy resin), Osaka Gas Chemicals "PG-100", "CG-500", Mitsubishi Chemical Corporation "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1031S" (tetraphenylethane type epoxy resin), "157S70" (bisphenol novolak type epoxy resin) ), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical, "PG-100", "CG-500" manufactured by Osaka Gas Chemicals, manufactured by Mitsubishi Chemical Corporation "YL7800" (fluorene type epoxy resin), "jER1031S" by Mitsubishi Chemical Corporation (tetraphenylethane type epoxy resin), etc. are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As the component (B), when a liquid epoxy resin and a solid epoxy resin are used in combination, their ratio (solid epoxy resin: liquid epoxy resin) is preferably in the range of 1:0.1 to 1:15 by mass. By setting the ratio of the liquid epoxy resin to the solid epoxy resin within this range, i) when used in the form of a resin sheet, adequate adhesion is brought about, and ii) when used in the form of a resin sheet, sufficient flexibility can be obtained, and handling The properties are improved, and effects such as iii) being able to obtain a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin: liquid epoxy resin) is more preferably in the range of 1:0.3 to 1:10 by mass ratio, 1: The range of 0.6 to 1:8 is more preferable.

The content of the epoxy resin having an aromatic structure in the resin composition is preferably 1% by mass or more, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, More preferably, it is 2 mass % or more, More preferably, it is 3 mass % or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention appears, Preferably it is 10 mass % or less, More preferably, it is 8 mass % or less, More preferably, it is 6 mass % or less.

In addition, the content of the epoxy resin having an aromatic structure in the resin composition, from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability, the nonvolatile components of the resin composition excluding the component (C) and the component (F) are 100 When it is set as mass %, it is 20 mass % or more, More preferably, it is 25 mass % or more, More preferably, it is 30 mass % or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention appears, Preferably it is 70 mass % or less, More preferably, it is 60 mass % or less, More preferably, it is 55 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, still more preferably 110 to 1000. By being in this range, the crosslinking density of hardened|cured material becomes sufficient and the insulating layer with small surface roughness can be formed. In addition, an epoxy equivalent can be measured according to JISK7236, and is the mass of resin containing 1 equivalent of an epoxy group.

The weight average molecular weight of the epoxy resin which has an aromatic structure becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of an epoxy resin is a weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography (GPC) method.

<(C) Thermally Conductive Filler>

The resin composition of this invention contains (C) a thermally conductive filler, and the average particle diameter of (C)component is 2.5 micrometers - 5.0 micrometers, and a specific surface area is 0.8 m<2>/g or more. By containing component (C) which has a predetermined average particle diameter and specific surface area, the insulating layer excellent in thermal conductivity and peeling strength can be obtained. Moreover, since the component (C) which has a predetermined average particle diameter and a specific surface area has a high dispersibility, the filling property of a resin varnish can be improved. Here, in this specification, a thermally conductive filler means the inorganic filler whose thermal conductivity is 20 W/m*K or more.

The material of component (C) is not particularly limited as long as the thermal conductivity is within the above range and has a predetermined average particle diameter and a predetermined specific surface area, for example, alumina, aluminum nitride, boron nitride, silicon carbide, etc. can Among these, alumina is particularly suitable. (C) A component may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, you may use combining 2 or more types of the same material.

(C) The average particle diameter of component is 2.5 micrometers - 5.0 micrometers from a viewpoint of improving the viewpoint of obtaining the insulating layer excellent in both thermal conductivity and peeling strength, and filling. (C) 2.5 micrometers - 4.8 micrometers are preferable and, as for the average particle diameter of component, 2.5 micrometers - 4.5 micrometers are more preferable. (C) The average particle diameter of component can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle size distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle size distribution analyzer, and making the intermediate diameter into an average particle diameter. As a measurement sample, what disperse|distributed (C)component in water with an ultrasonic wave can be used preferably. As a laser diffraction scattering type particle size distribution analyzer, "LA-500" by Horiba Corporation, "SALD2200" by Shimadzu Corporation, etc. can be used. Specifically, it can measure according to the method as described in <Measurement of the average particle diameter of a thermally conductive filler> mentioned later.

(C) The specific surface area of component is 0.8 m<2>/g or more from a viewpoint of obtaining the insulating layer excellent in both thermal conductivity and peeling strength, and a viewpoint of improving fillability. (C) The specific surface area of the component is preferably 0.8 m 2 /g to 10 m 2 /g, more preferably 0.8 m 2 /g to 5 m 2 /g. (C) The specific surface area of a component can be measured by nitrogen BET method. Specifically, it can be measured using an automatic specific surface area measuring device, and as the automatic specific surface area measuring device, "Macsorb HM-1210" manufactured by Muntech Corporation, etc. can be used. Specifically, it can measure according to the method described in <Measurement of the specific surface area of a thermally conductive filler> mentioned later.

(C) The component may be surface-treated with a surface treating agent from a viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include 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 a titanate-based coupling agent. there is. As a commercial item of a surface treatment agent, Shin-Etsu Chemical Co., Ltd. make "KBM403" (3-glycidoxypropyl trimethoxysilane), Shin-Etsu Chemical Co., Ltd. make "KBM803" (3-mercaptopropyltrimethoxy), for example, silane), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by Kogyo Corporation, "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane couple) ring agent) and the like. A surface treatment agent may be used individually by 1 type, and may use 2 or more types.

(C) When content of component makes 100 mass % of non-volatile components in a resin composition from a viewpoint of obtaining the insulating layer excellent in both thermal conductivity and peeling strength, Preferably it is 87 mass % or more, More preferably, it is 88 mass %. It is mass % or more, More preferably, it is 89 mass % or more, or 90 mass % or more. An upper limit becomes like this. Preferably it is 95 mass % or less, More preferably, it is 93 mass % or less, More preferably, it is 92 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 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, a cyanate ester-based curing agent, and carbodiimide-based curing agents. A hardening|curing agent may be used individually by 1 type, or may use 2 or more types together. (D) component is preferably at least one 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 at least one selected from a phenol-based curing agent and an active ester-based curing agent desirable.

As the phenol-based curing agent and the naphthol-based curing agent, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable. Moreover, a nitrogen-containing phenolic hardening|curing agent is preferable from an adhesive viewpoint with a wiring layer, and a triazine skeleton containing phenolic hardening|curing agent is more preferable. Among 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 naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei, "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku. , "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" manufactured by Shin-Nittetsu Sumikin, "TD-2090" manufactured by DIC, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500”, “HPC-9500”, “KA-1160”, “KA-1163”, "KA-1165", "GDP-6115L" by Gunei Chemical Company, "GDP-6115H", etc. are mentioned.

From the viewpoint of obtaining an insulating layer excellent in adhesion to the metal layer, an active ester curing agent is also preferable. Although there is no restriction|limiting in particular as an active ester type hardening|curing agent, Generally, ester groups with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters, are 2 in 1 molecule. Compounds having at least one compound are preferably used. It is preferable that the said active ester type hardening|curing agent is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound, 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, and pyromellic acid. 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, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol to one molecule of dicyclopentadiene.

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 a benzoyl product of phenol novolac. An active ester compound is preferable, and among these, the active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structure comprising phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents are active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM" ", "EXB-8000L-65TM" (manufactured by DIC), "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure, and "DC808" as an active ester compound containing an acetylated product of phenol novolac ” (manufactured by Mitsubishi Chemical Corporation), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoyl product of phenol novolac, and “DC808” (Mitsubishi Kaga) as an active ester curing agent that is an acetylated product of phenol novolac "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc. are mentioned as an active ester curing agent which is a benzoyl product of phenol novolac. .

As a specific example of a benzoxazine type hardening|curing agent, "HFB2006M" by a Showa Kobunshi company, "P-d" by a Shikoku Kasei Co., Ltd. product, and "F-a" are mentioned.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6- Dimethylphenyl cyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4- cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cya Difunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, etc., these cyanate resins are partially triazined A prepolymer etc. are mentioned. As a specific example of a cyanate ester type hardening|curing agent, "PT30" and "PT60" (all are phenol novolak-type polyfunctional cyanate ester resin), "BA230", "BA230S75" (a part of bisphenol A dicyanate by Ronza Japan) or a prepolymer in which all of them were triazined and trimer) and the like.

As a specific example of a carbodiimide type hardening|curing agent, "V-03", "V-07" by Nisshinbo Chemicals, etc. are mentioned.

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 nonvolatile component in the resin composition is 100% by mass, preferably 5% by mass or less, more preferably It is 3 mass % or less, More preferably, it is 2 mass % or less. Moreover, although there is no restriction|limiting in particular as for a minimum, 0.1 mass % or more is preferable, and 0.5 mass % or more is more preferable.

<(E) curing accelerator>

The resin composition of this invention can contain (E) a hardening accelerator. Examples of the curing accelerator include a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, a guanidine curing accelerator, and a metal curing accelerator, and a phosphorus curing accelerator, an amine curing accelerator, and imidazole curing accelerator. An accelerator and a metal-type hardening accelerator are preferable, and an amine-type hardening accelerator, an imidazole-type hardening accelerator, and a metal-type hardening accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphoniumdecanoate, (4-methylphenyl)triphenyl Phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc. are mentioned, Triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8 -diazabicyclo(5,4,0)-undecene etc. are mentioned, 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, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 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-triazineisocyanuric acid adduct, 2-phenylimidazolisonuric acid adduct, 2 -Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a] Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and an adduct of an imidazole compound and an epoxy resin and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As an imidazole-type hardening accelerator, you may use a commercial item, for example, "P200-H50" by a Mitsubishi Chemical Company, etc. are mentioned.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. are mentioned, dicyandiamide, 1,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, and a tin, is mentioned, for example. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II)acetylacetonate and cobalt(III)acetylacetonate, organocopper complexes such as copper(II)acetylacetonate, zinc(II)acetylacetonate, and the like. organic zinc complexes, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

When a resin composition contains (E) component, content of the hardening accelerator in a resin composition is although it does not specifically limit, When the non-volatile component in a resin composition is 100 mass %, 0.01 mass % - 1 mass % are preferable.

<(F) Inorganic filler (excluding those corresponding to component (C))>

The resin composition of the present invention may contain (F) an inorganic filler. (F) The material of the component is not particularly limited, and for example, silica, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, Barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, etc. are mentioned. Among these, silica is particularly suitable. Moreover, as a silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

The average particle diameter 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 properties and obtaining an insulating layer with low surface roughness; More preferably, it is 2 micrometers or less. Although the lower limit of the said average particle diameter is not specifically limited, Preferably it is 0.01 micrometer or more, More preferably, it is 0.05 micrometer or more, More preferably, it is 0.1 micrometer or more. The average particle diameter of an inorganic filler can be measured similarly to (C)component. As a commercial item of the inorganic filler which has such an average particle diameter, "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatex Corporation, "UFP-30" manufactured by Denki Chemical Co., Ltd. are, for example, , "Seal-Fill NSS-3N", "Seal-Fill NSS-4N", and "Seal-Fill NSS-5N" manufactured by Toyama Corporation, "SC2500SQ", "SO-C6", "SO-C4", and " SO-C2", "SO-C1", etc. are mentioned.

From the viewpoint of improving 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 a titanate-based coupling agent. It is preferable that it is processed with 1 or more types of surface treatment agents, such as a coupling agent. The commercial items of a specific surface treatment agent, etc. are as above-mentioned.

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 nonvolatile component in the resin composition is 100% by mass, preferably 0.1% by mass or more, more Preferably it is 0.5 mass % or more, More preferably, it is 1 mass % or more. An upper limit becomes like this. Preferably it is 5 mass % or less, More preferably, it is 4 mass % or less, More preferably, it is 3 mass % or less.

<(G) Flame Retardant>

The resin composition may include (G) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

As a flame retardant, you may use a commercial item, for example, "HCA-HQ" by Sanko Corporation, "PX-200" by Daihachi Chemical Industry Co., Ltd., "SPH-100" by Otsuka Chemicals, "SPS" -100", "SPB-100", "SPE-100", "FP-100", "FP-110", "FP-300", and "FP-400" manufactured by Fushimi Seiyakusho. there is.

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

<(H) optional additives>

The resin composition may further contain other additives as needed. Examples of such other additives include organometallic compounds such as an organocopper compound, an organozinc compound and an organocobalt compound, and a binder, a thickener, an antifoaming agent, Resin additives, such as a leveling agent, an adhesion-imparting agent, and a coloring agent, etc. are mentioned.

<Physical properties of the resin composition>

The hardened|cured material which thermosetted the resin composition of this invention at 180 degreeC for 90 minute(s) shows the characteristic that it is excellent in the peeling strength with a metal layer. In detail, after laminating|stacking the resin composition of this invention on a metal layer, when it thermosets at 180 degreeC for 90 minute(s), it shows the characteristic that it is excellent in the peeling strength of hardened|cured material and a metal layer. As peeling strength, Preferably it is 0.4 kgf/cm or more, More preferably, it is 0.45 kgf/cm or more, More preferably, it is 0.5 kgf/cm or more. In addition, although the upper limit in particular of peeling strength is not limited, It can be set as 1.5 kgf/cm or less, 1 kgf/cm or less, etc. Evaluation of peeling strength can be measured according to the method as described in <The measurement and evaluation of the peeling strength (peel strength) of copper foil> mentioned later.

As a metal layer, Preferably it is a metal layer containing copper, More preferably, it is an electrolytic copper foil.

The cured product obtained by thermosetting the resin composition of the present invention at 180° C. for 90 minutes exhibits 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 still more preferably 2.0 W/m·K or more. The upper limit of the thermal conductivity can be 5.0 W/m·K or less, 4.0 W/m·K or less, or 3.5 W/m·K or less. Evaluation of thermal conductivity can be measured according to the method as described in <Measurement of thermal conductivity of hardened|cured material> mentioned later.

The resin composition of this invention can form the insulating layer excellent in thermal conductivity and peeling strength, Compatibility of (A) component is favorable by including (B) component. Therefore, the resin composition of the present invention is a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer of a semiconductor chip package), a resin composition for forming an insulating layer of a circuit board (including a printed wiring board) ( A resin composition for forming an interlayer insulating layer on which a conductor layer is formed by plating, which can be suitably used as a resin composition for an insulating layer of a circuit board (resin for an interlayer insulating layer of a circuit board on which a conductor layer is formed by plating) composition) can be more suitably used.

The resin composition of the present invention can also be suitably used as a resin composition for sealing a semiconductor chip (resin composition for sealing semiconductor chip), and a resin composition for forming wiring in a semiconductor chip (resin composition for forming wiring on a semiconductor chip). .

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 0.20 or more More preferably, it is more preferable to satisfy 0.25 or more. Although it does not specifically limit about a lower limit, It is preferable to satisfy 0.60 or less, It is more preferable to satisfy 0.55 or less, It is more preferable to satisfy 0.50 or less. Here, the high molecular weight component means the resin component contained in the resin composition with a weight average molecular weight of 10000 or more, and the low molecular weight component means the resin component contained in the resin composition whose weight average molecular weight is 5000 or less. The measuring method of a weight average molecular weight is as above-mentioned.

[Resin Sheet]

The resin sheet of this invention consists of a support body and the resin composition layer joined with the said support body, and a resin composition layer consists of the resin composition of this invention.

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 from the viewpoint of reducing the thickness. is below. Although the lower limit of the thickness of a resin composition layer is not specifically limited, Usually, 1 micrometer or more, 5 micrometers or more, 10 micrometers or more, etc. can be made.

As a support body, the film which consists of a plastic material, metal foil, and a release paper are mentioned, for example, The film which consists of a plastic material, and metal foil are preferable.

When a film made of a plastic material is used as the support, the plastic material is, for example, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), polyethylene naphthalate (hereinafter abbreviated as "PEN"). Polyester such as ), polycarbonate (hereinafter, may be abbreviated as “PC”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide ( PES), polyether ketone, polyimide, etc. are mentioned. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, or a foil made of an alloy of copper and other metals (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good.

A support body may give the surface to join with the resin composition layer a mat|matte process and corona treatment.

Moreover, as a support body, you may use the support body with a mold release layer which has a mold release layer on the surface to join with the resin composition layer. As a mold release agent used for the mold release layer of a support body with a mold release layer, 1 or more types of mold release agents are mentioned from the group which consists of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin, for example. A commercial item may be used for the support body with a release layer, for example, "SK-1", "AL-5", "AL-" manufactured by Lintec which is a PET film which has a release layer which has an alkyd resin type mold release agent as a main component. 7", "Lumira T60" by Toray Corporation, "Purex" by Teijin Corporation, "Uni-pil" by Unichika Corporation, etc. are mentioned.

Although it does not specifically limit as thickness of a support body, The range of 5 micrometers - 75 micrometers is preferable, and the range of 10 micrometers - 60 micrometers is more preferable. Moreover, when using a support body with a mold release layer, it is preferable that the thickness of the whole support body with a mold release layer is the said range.

The resin sheet can be produced by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish to a support using a die coater or the like, and further drying to form a resin composition layer. .

Since the resin composition of the present invention contains (C) a thermally conductive filler, even if the resin varnish has a solid content concentration of 85% by mass or more, it can be applied on a support or the like, and can be molded into a sheet shape, that is, excellent filling properties. indicates characteristics. 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. The lower limit is not particularly limited, but may be 0.01 Pa·s or more. The viscosity of the resin varnish is the value measured with the E-type viscometer at 25 degreeC.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butylcarbitol; aromatic hydrocarbons such as toluene and xylene; and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

You may perform drying by well-known methods, such as a heating and hot air spraying. Although drying conditions are not specifically limited, Content of the organic solvent in a resin composition layer is 10 mass % or less, Preferably it is made to dry so that it may become 5 mass % or less. Although it depends also on the boiling point of the organic solvent in a resin varnish, for example, when using the resin varnish containing 30 mass % - 60 mass % of an organic solvent, by drying at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes, the resin A composition layer can be formed.

In the resin sheet, a protective film conforming 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 on the opposite side to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer - 40 micrometers. By laminating|stacking a protective film, adhesion of dust, etc. to the surface of a resin composition layer, and a flaw can be prevented. The resin sheet can be wound and stored in a roll shape. When a resin sheet has a protective film, it becomes usable by peeling off a 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-like fiber base material used for the prepreg is not particularly limited, and those commonly used as the base material for prepregs, such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of reduction in thickness, the thickness of the sheet-like 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. Although the lower limit of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it can be set as 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more.

A prepreg can be manufactured by well-known methods, such as a hot melt method and a solvent method.

The thickness of a prepreg can be made into the range similar to the resin composition layer in an above-mentioned resin sheet.

The resin sheet of this invention can be used suitably in manufacture of a semiconductor chip package, in order to form an insulating layer (resin sheet for insulation of 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 insulating layer on which a conductor layer is formed by plating In order to form (for the interlayer insulating layer of a circuit board which forms a conductor layer by plating), it can use more suitably. Examples of the package 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 sealing a semiconductor chip (resin sheet for sealing semiconductor chip) or for forming wiring in a semiconductor chip (resin sheet for forming wiring for semiconductor chip), for example, For example, it can be suitably used for a fan-out type WLP (Wafer Level Package), a fan-in type WLP, a fan-out type PLP (Panel Level Package), and a fan-in type PLP. Moreover, it can be used suitably also for the MUF (Molding Under Filling) material etc. which are used after connecting a semiconductor chip to a board|substrate.

Furthermore, the resin sheet of this invention can be used suitably in order to form the insulating layer of circuit boards, such as another wide use which high insulation reliability is calculated|required, for example, printed wiring boards.

[circuit board]

The circuit board of this invention contains the insulating layer formed with the hardened|cured material of the resin composition of this invention.

The manufacturing method of the circuit board of this invention,

(1) a step of preparing a substrate with a wiring layer, which has a substrate and a wiring layer as a metal layer formed on at least one surface of the substrate;

(2) the process of laminating|stacking the resin sheet of this invention on a base material with a wiring layer so that a wiring layer may be embedded in the resin composition layer, thermosetting it, and forming an insulating layer;

(3) A step of interconnecting the wiring layers between layers is included. Moreover, the manufacturing method of a circuit board may include the process of (4) removing a base material.

The step (3) is not particularly limited as long as a wiring layer other than the wiring layer as a metal layer can be interconnected between layers, but a via hole is formed in the insulating layer to form a wiring layer, and the insulating layer is polished or ground to expose the wiring layer It is preferable that it is at least any one process of the process to make.

<Process (1)>

Step (1) is a step of preparing a substrate with a wiring layer, which includes a substrate and a wiring layer formed on at least one surface of the substrate. Usually, a board|substrate with a wiring layer has a 1st metal layer and a 2nd metal layer which are a part of a base material on both surfaces of a base material, respectively, It has a wiring layer in the surface on the opposite side to the surface on the side of a base material of a 2nd metal layer. In detail, a dry film (photosensitive resist film) is laminated|stacked on a base material, it exposes and develops under predetermined conditions using a photomask, and a pattern dry film is formed. After forming a wiring layer by the electrolytic plating method using the developed pattern dry film as a plating mask, the pattern dry film is peeled. Moreover, it is not necessary to have a 1st metal layer and a 2nd metal layer.

Examples of the substrate include substrates such as glass epoxy substrates, metal substrates (stainless steel or cold rolled steel sheet (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. and metal layers, such as copper foil, may be formed in the board|substrate surface. Moreover, metal layers, such as a 1st metal layer and a 2nd metal layer (For example, Mitsui Kinzoku Corporation ultra-thin copper foil with carrier copper foil, brand name "Micro Thin") which can be peeled, may be formed in the surface.

The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, and for example, dry films such as novolac resin and acrylic resin can be used. A commercial item may be used for a dry film.

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

After laminating a dry film on a substrate, exposure and development are performed under predetermined conditions using a photomask for forming 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 (ie, the pitch is 40 µm or less), more preferably 10/10 µm or less, further Preferably it is 5/5 micrometer or less, More preferably, it is 1/1 micrometer or less, Especially preferably, it is 0.5/0.5 micrometer or more. The pitch need not be the same throughout the wiring layer. The minimum pitch of the wiring layers 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, formation of a wiring layer can be performed by the plating method using the dry film in which the desired pattern was formed as a plating mask.

The conductor material used for the wiring layer is not specifically limited. In a suitable embodiment, the wiring layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. . The wiring layer may be a single metal layer or an alloy layer, and the alloy layer is, for example, an alloy of two or more metals selected from the group described above (eg, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). ) formed from Among these, from the viewpoint of versatility of wiring layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper-nickel alloy, copper - An alloy layer of a titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy layer is more preferable, and a single metal layer of copper is still more preferable.

The thickness of the wiring layer depends on the desired design of the wiring board, but is preferably 3 µm to 35 µm, more preferably 5 µm to 30 µm, still more preferably 10 µm to 20 µm, or 15 µm. In the case of employing a step of grinding or grinding the insulating layer to expose the wiring layer to interconnect a wiring layer different from the wiring layer as a metal layer in the step (3), the thickness of the wiring to be connected between the layers and the wiring not to be connected should be different. desirable. The thickness of the wiring layer can be adjusted by repeating the above-described pattern formation. Although the thickness of the wiring layer (conductive filler) with the greatest thickness among each wiring layer depends on the design of a desired wiring board, Preferably it is 100 micrometers or less and 2 micrometers or more. Moreover, the wiring for interlayer connection may be made into a convex type.

After forming the wiring layer, the dry film is peeled off. Peeling of a dry film can be performed using alkaline peeling liquids, such as a sodium hydroxide solution, for example. If necessary, unnecessary wiring patterns may be removed by etching or the like to form a desired wiring pattern. About the pitch of the wiring layer to form, it is as above-mentioned.

<Process (2)>

Process (2) is a process of laminating|stacking the resin sheet of this invention on a base material with a wiring layer so that a wiring layer may be embedded in the resin composition layer, thermosetting it, and forming an insulating layer. In detail, the wiring layer of the base material with a wiring layer obtained in said process (1) is laminated|stacked so that it may be embedded in the resin composition layer of a resin sheet, and the resin composition layer of a resin sheet is thermosetted, and the insulating layer is formed.

After removing the protective film of a resin sheet, lamination|stacking of a wiring layer and a resin sheet can be performed by thermocompression-bonding a resin sheet to a wiring layer from the support body side, for example. As a member (hereinafter also referred to as a "thermocompression bonding member") which heat-compresses a resin sheet to a wiring layer, a heated metal plate (SUS end plate etc.), a metal roll (SUS roll), etc. are mentioned, for example. In addition, it is preferable not to press the thermocompression-bonding member directly to a resin sheet, but to press through elastic materials, such as a heat-resistant rubber, so that a resin sheet may fully follow the surface unevenness|corrugation of a wiring layer.

You may perform lamination|stacking of a wiring layer and a resin sheet by the vacuum lamination method after removing the protective film of a resin sheet. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the thermocompression compression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably It is the range of 0.29 MPa - 1.47 MPa, and thermocompression bonding time becomes like this. Preferably it is 20 second - 400 second, More preferably, it is the range of 30 second - 300 second. Lamination is preferably performed under reduced pressure conditions of a pressure of 13 hPa or less.

After lamination, the laminated resin sheet may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing the thermocompression-bonding member from the support side. The press conditions of the smoothing process can be made into the conditions similar to the thermocompression-bonding conditions of the said lamination|stacking. In addition, you may perform lamination|stacking and a smoothing process continuously using the above-mentioned commercially available vacuum laminator.

After laminating a resin composition layer on a substrate with a wiring layer so that the wiring layer is embedded, the resin composition layer is thermosetted to form an insulating layer. For example, although the thermosetting conditions of the resin composition layer vary depending on the type of resin composition, etc., 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 thermosetting a resin composition layer, you may preheat a resin composition layer at temperature lower than hardening temperature.

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

<Process (3)>

Step (3) is a step of interconnecting the wiring layers between layers. In detail, it is a process of forming a via hole in an insulating layer, forming a conductor layer, and connecting a wiring layer between layers. Alternatively, the insulating layer is polished or ground, the wiring layer is exposed, and the wiring layer other than the metal layer is interconnected between layers.

In the case of employing a process of forming a via hole in the insulating layer and forming a conductor layer to connect the wiring layers between layers, the formation of the via hole is not particularly limited, but laser irradiation, etching, mechanical drilling, etc. are mentioned. It is preferably done by Such laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas laser, a YAG laser, an excimer laser, or the like as a light source. In detail, laser irradiation is performed from the surface side of the support body of the resin sheet, and the via hole which penetrates the support body and an insulating layer and exposes a wiring layer is formed.

Conditions for laser irradiation are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.

Although the shape of the via hole, ie, the shape of the outline of the opening seen in the extending direction, is not specifically limited, Generally, it is set as circular (approximately circular).

After the via hole formation, a so-called desmear process, which is a smear removal process in the via hole, may be performed. When formation of the conductor layer mentioned later is performed by a plating process, you may perform a wet desmear process with respect to a via hole, for example, When formation of a conductor layer is performed by a sputtering process, for example, plasma You may perform dry desmear processes, such as a treatment process. In addition, a desmear process may serve also as a roughening process process.

Before forming a conductor layer, you may perform a roughening process with respect to a via hole and an insulating layer. A well-known procedure and conditions normally performed can be employ|adopted for a roughening process. Plasma processing etc. are mentioned as an example of a dry roughening process, As an example of a wet roughening process, the swelling process by a swelling liquid, the roughening process by an oxidizing agent, and the method of performing the neutralization process by a neutralization liquid in this order are mentioned.

After the via hole is formed, a conductor layer is formed. The conductor material constituting the conductor layer is not particularly limited, and the conductor layer can be formed by any suitable method known in the art, such as plating, sputtering, and vapor deposition, and is preferably formed by plating. In a suitable embodiment, for example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full additive method. Moreover, when the support body in a resin sheet is metal foil, the conductor layer which has a desired wiring pattern can be formed by conventionally well-known techniques, such as a subtractive method. The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated.

Specifically, the plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern for exposing a portion of the plating seed layer in correspondence to a desired wiring pattern is formed. An electrolytic plating layer is formed by electrolytic plating on the exposed plating seed layer. At this time, with the formation of the electrolytic plating layer, the filled via may be formed by filling the via hole by electrolytic plating. After the electrolytic plating layer is formed, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern. In addition, when forming a conductor layer, the dry film used for formation of a mask pattern is the same as that of the said dry film.

The conductor layer may include, for example, an electrode pad (land) on which an external terminal can be mounted, as well as an on-line wiring. In addition, the conductor layer may be comprised only with the electrode pad.

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.

In the case of employing a step of grinding or grinding the insulating layer and exposing the wiring layer as a metal layer to connect the wiring layer different from the metal layer between layers, the wiring layer can be exposed as a polishing method or grinding method of the insulating layer, It is not particularly limited as long as it is horizontal, and a conventionally known polishing method or grinding method can be applied. For example, a chemical mechanical polishing method using a chemical mechanical polishing apparatus, a mechanical polishing method such as buffing, or a surface grinding by rotating a whetstone method and the like. Similar to the process of forming a via hole in an insulating layer, forming a conductor layer, and connecting wiring layers between layers, the smear removal process and the process of performing a roughening process may be performed, and a conductor layer may be formed. In addition, it is not necessary to expose all the wiring layers as metal layers, and you may expose a part of wiring layers as metal layers.

<Process (4)>

A process (4) is a process of removing a base material and forming the circuit board of this invention. The method of removing the substrate is not particularly limited. In one suitable embodiment, the substrate is peeled from the circuit board at the interface between the first and second metal layers, and the second metal layer is etched away with, for example, an aqueous copper chloride solution or the like. If necessary, you may peel a board|substrate in the state which protected the conductor layer with the protective film.

[Semiconductor Chip Package]

A first aspect of the semiconductor chip package of the present invention is a semiconductor chip package in which a semiconductor chip is mounted on the circuit board of the present invention. A semiconductor chip package can be manufactured by bonding a semiconductor chip to the circuit board of the said invention.

As long as the terminal electrode of the semiconductor chip is conductor-connected to the circuit wiring of the circuit board, bonding conditions are not particularly limited, and well-known conditions used in flip-chip mounting of the semiconductor chip may be used. Moreover, you may join between a semiconductor chip and a circuit board through an insulating adhesive agent.

One suitable embodiment presses the semiconductor chip to the circuit board. As the crimping conditions, for example, the crimping temperature is in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the crimping time is in the range of 1 second to 60°C. It can be set as the range of seconds (preferably from 5 seconds to 30 seconds).

Another preferred embodiment is to reflow and bond the semiconductor chip to the circuit board. As reflow conditions, it can be set as the range of 120 degreeC - 300 degreeC, for example.

After bonding the semiconductor chip to the circuit board, it is also possible to obtain a semiconductor chip package by, for example, filling the semiconductor chip with a mold underfill material. The method of filling with a mold underfill material can be implemented by a well-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 as an example is the semiconductor chip package which manufactured the sealing layer 120 with the resin composition or resin sheet of this invention. The semiconductor chip package 100 includes a semiconductor chip 110 , a sealing layer 120 formed to cover the periphery of the semiconductor chip 110 , and redistribution on a surface opposite to the side covered by the sealing layer of the semiconductor chip 110 . A forming layer (insulating layer) 130 , a conductor layer (rewiring layer) 140 , a solder resist layer 150 , and bumps 160 are provided. The manufacturing method of such a semiconductor chip package,

(A) a step of laminating a temporarily fixed film on the substrate,

(B) the step of temporarily fixing the semiconductor chip on the temporarily fixing film,

(C) the process of laminating|stacking the resin composition layer of the resin sheet of this invention on a semiconductor chip, or apply|coating the resin composition of this invention on a semiconductor chip, thermosetting, and forming a sealing layer;

(D) the step of peeling the substrate and the temporarily fixed film from the semiconductor chip,

(E) a step of forming a redistribution forming layer (insulating layer) on the surface of the semiconductor chip, the substrate and the temporarily fixed film,

(F) forming a conductor layer (rewiring layer) on the redistribution forming layer (insulating layer); and

(G) The process of forming a soldering resist layer on a conductor layer is included. Moreover, the manufacturing method of a semiconductor chip package may include the process of (H) dicing a some semiconductor chip package into individual semiconductor chip package, and dividing it into pieces.

<Process (A)>

Process (A) is a process of laminating|stacking a temporarily fixed film on a base material. Lamination conditions of a base material and a temporarily fixed film are the same as the lamination|stacking conditions of the wiring layer and resin sheet in the process (2) in the manufacturing method of a circuit board, and a preferable range is also the same.

The material used for the base material is not particularly limited. Examples of the substrate include a silicon wafer; glass wafer; glass substrate; metal substrates such as copper, titanium, stainless steel, and cold rolled steel sheet (SPCC); a substrate (eg, FR-4 substrate) in which glass fibers are impregnated with an epoxy resin and subjected to thermosetting treatment; The board|substrate etc. which consist of bismaleimide triazine resin (BT resin) are mentioned.

Temporarily fixing film, while being able to peel from a semiconductor chip in the process (D) mentioned later, if a semiconductor chip can be temporarily fixed, a material is not specifically limited. A commercial item can be used for a temporarily fixed film. As a commercial item, the Nitto Denko Co., Ltd. River Alpha etc. are mentioned.

<Process (B)>

A process (B) is a process of temporarily fixing a semiconductor chip on a temporarily fixing film. Temporarily fixing a semiconductor chip can be performed using well-known apparatuses, such as a flip chip bonder and a die bonder. The layout and the number of arrangement of the semiconductor chip can be appropriately set according to the shape, size, number of production of the target semiconductor package, etc. of the temporarily fixed film, for example, a plurality of rows, and arranged in a matrix form of a plurality of columns, can be fixed temporarily.

<Process (C)>

A process (C) is a process of laminating|stacking the resin composition layer of the resin sheet of this invention on a semiconductor chip, or apply|coating the resin composition of this invention on a semiconductor chip, thermosetting, and forming a sealing layer. At a process (C), it is preferable to laminate|stack the resin composition layer of the resin sheet of this invention on a semiconductor chip, thermoset it, and form a sealing layer.

After removing the protective film of a resin sheet, lamination|stacking of a semiconductor chip and a resin sheet can be performed by thermocompression-bonding a resin sheet to a semiconductor chip from the support body side, for example. As a member (henceforth a "thermal compression bonding member") which heat-compresses a resin sheet to a semiconductor chip, a heated metal plate (SUS hard plate etc.), a metal roll (SUS roll), etc. are mentioned, for example. In addition, it is preferable to press through an elastic material, such as a heat-resistant rubber, so that a resin sheet may fully follow the surface unevenness|corrugation of a semiconductor chip, rather than directly pressing a thermocompression-bonding member to a resin sheet.

In addition, you may perform lamination|stacking of a semiconductor chip and a resin sheet by the vacuum lamination method after removing the protective film of a resin sheet. The lamination conditions in the vacuum lamination method are the same as the lamination conditions of the wiring layer and the resin sheet in the step (2) in the circuit board manufacturing method, and the preferable ranges are also the same.

The support body of a resin sheet may peel after laminating|stacking a resin sheet on a semiconductor chip and thermosetting, and may peel a support body before laminating|stacking a resin sheet on a semiconductor chip.

As application|coating conditions of a resin composition, it is the same as the application|coating conditions at the time of forming the resin composition layer in the resin sheet of this invention, and a preferable range is also the same.

<Process (D)>

A process (D) is a process of peeling a base material and a temporarily fixed film from a semiconductor chip. The peeling method can be appropriately changed depending on the material of the temporarily fixed film, etc., for example, by heating the temporarily fixed film, foaming (or expanding) to peel the method, and irradiating ultraviolet rays from the substrate side, the temporarily fixed film The method of reducing adhesive force and peeling, etc. are mentioned.

In the method of peeling the temporarily fixed film by heating, foaming (or expanding), heating conditions are usually at 100 ° C. to 250 ° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method of irradiating an ultraviolet ray from the base material side and peeling by reducing the adhesive force of a temporarily fixed film, the irradiation amount of an ultraviolet-ray is 10mJ/cm<2> - 1000mJ/cm<2> normally.

<Process (E)>

A process (E) is a process of forming a redistribution forming layer (insulating layer) in the surface which peeled the base material and temporarily fixed film of a semiconductor chip.

The material for forming the redistribution forming layer (insulating layer) is not particularly limited as long as it has insulating properties when the redistribution forming layer (insulating layer) is formed. Do. As a thermosetting resin, you may use the resin composition of the same composition as the resin composition for forming the resin sheet of this invention.

After formation of the redistribution forming layer (insulating layer), a via hole may be formed in the redistribution forming layer (insulating layer) for interlayer connection between a semiconductor chip and a conductor layer to be described later.

In forming the via hole, when the material forming the redistribution forming layer (insulating layer) is a photosensitive resin, first, the surface of the redistribution forming layer (insulating layer) is irradiated with active energy rays through a mask pattern, and the The wiring layer is photocured.

As an active energy ray, an ultraviolet-ray, a visible ray, an electron beam, X-ray etc. are mentioned, for example, Especially an ultraviolet-ray is preferable. The irradiation amount of ultraviolet rays and irradiation time can be suitably changed according to the photosensitive resin. The exposure method is either a contact exposure method in which the mask pattern is exposed in close contact with the redistribution forming layer (insulating layer), or a non-contact exposure method in which the mask pattern is exposed using parallel light without being in close contact with the redistribution forming layer (insulating layer). may be used.

Next, the rewiring forming layer (insulating layer) is developed and an unexposed portion is removed to form a via hole. For development, either wet development or dry development is suitable. A well-known developing solution can be used for the developing solution used by wet image development.

As a method of image development, a dip method, a paddle method, a spray method, a brushing method, a scraping method etc. are mentioned, for example, From a viewpoint of resolution, a paddle method is suitable.

When the material for forming the redistribution forming layer (insulating layer) is a thermosetting resin, the formation of the via hole is not particularly limited, and laser irradiation, etching, mechanical drilling, etc. are mentioned, but it is preferably performed by laser irradiation. Laser irradiation can be performed using any suitable laser processing machine which uses a carbon dioxide gas laser, a UV-YAG laser, an excimer laser, etc. as a light source.

Conditions for laser irradiation are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.

Although the shape of the via hole, ie, the shape of the outline of the opening seen in the extending direction, is not specifically limited, Generally, it is set as circular (approximately 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. Although a lower limit is not specifically limited, Preferably it is 10 micrometers or more, More preferably, it is 15 micrometers or more, More preferably, it is 20 micrometers 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 redistribution forming layer (insulating layer) is the same as the method of forming the conductor layer after forming a via hole in the insulating layer in step (3) in the circuit board manufacturing method, and the preferred range is also same. Further, the steps (E) and (F) may be repeated, and a conductor layer (rewiring layer) and a rewiring forming layer (insulating layer) may be alternately stacked (build-up).

<Process (G)>

A process (G) is a process of forming a soldering resist layer on a conductor layer.

The material which forms a soldering resist layer will not be specifically limited if it has insulation at the time of soldering resist layer formation, A viewpoint of the ease of manufacture of a semiconductor chip package to photosensitive resin and thermosetting resin are preferable. As a thermosetting resin, you may use the resin composition of the same composition as the resin composition for forming the resin sheet of this invention.

In addition, in a process (G), you may perform the bumping process which forms a bump as needed. The bumping process can be performed by a well-known method, such as a solder ball and solder plating. In addition, formation of a via hole in a bumping process can be performed similarly to a process (E).

<Process (H)>

The manufacturing method of a semiconductor chip package may include the process (H) in addition to the process (A) - the process (G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into pieces.

The method of dicing a semiconductor chip package into each semiconductor chip package is not specifically limited, A well-known method can be used.

The 3rd aspect of the semiconductor chip package of this invention is the redistribution formation layer (insulation layer) 130 in a semiconductor chip package (Fan-out type WLP) as an example is shown in FIG. 1, for example, and a soldering resist layer, for example. (150) is a semiconductor chip package made of the resin composition or resin sheet of the present invention.

[Semiconductor device]

Examples of the semiconductor device on which the semiconductor chip package of the present invention is to be mounted include electric appliances (e.g., computers, mobile phones, smartphones, tablet-type devices, wearable devices, digital cameras, medical devices, televisions, etc.) and vehicles ( For example, various semiconductor devices provided in motorcycles, automobiles, electric vehicles, ships, aircraft, etc.) may be mentioned.

[Example]

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, in the following description, "part" and "%" mean "part by mass" and "mass %", respectively, unless otherwise indicated.

<Preparation of sample for measuring peel strength>

(1) Underlay treatment of inner-layer circuit board

The copper surface roughening treatment was performed by immersing both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 µm, substrate thickness 0.3 mm, R5715ES manufactured by Panasonic) in CZ8100 manufactured by Meg Corporation on which the inner-layer circuit was formed.

(2) Preparation of resin sheet

PET film (“Lumira R80” manufactured by Toray Co., Ltd., thickness 38 μm, softening point 130° C., or less; "Releasable PET" in some cases), it applied with a die coater so that the thickness of the resin composition layer after drying might be set to 100 micrometers, and it dried at 80 degreeC - 100 degreeC (average 90 degreeC) for 7 minutes, and the resin sheet was obtained.

(3) Lamination of resin sheets

The produced resin sheet was laminated on both surfaces of the inner circuit board so that the resin composition layer was bonded to the inner circuit board using a batch vacuum pressurization laminator (a two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.). Lamination|stacking was performed by pressure-reducing for 30 second and making atmospheric|air pressure 13 hPa or less, and then crimping|bonding for 30 second at 120 degreeC and pressure 0.74 Mpa. Then, it hot-pressed for 60 second at 120 degreeC and the pressure of 0.5 MPa.

(4) Lamination with metal layer (copper foil)

Thereafter, the support is peeled off and the roughened surface of the resin composition layer and the electrodeposited copper foil is bonded to the exposed surface of the resin composition layer, so that the electrolytic copper foil (“JTCP” manufactured by JX Nikko Nisseki Kinzoku Co., Ltd., 35 μm thick, roughened surface The maximum height (Rz: JIS B0601-2001): 6 µm) was laminated. Then, it laminated|stacked under the same conditions using the said laminator apparatus.

(5) curing of the resin composition

After lamination|stacking, the resin composition layer was hardened|cured on 180 degreeC and hardening conditions for 90 minutes.

<Measurement and evaluation of peel strength (peel strength) of copper foil>

A partial incision with a width of 10 mm and a length of 100 mm is made in the electrolytic copper foil, and this end is peeled off and held with tongs (Autocom-type testing machine "AC-50C-SL" manufactured by TS Corporation) at room temperature at a speed of 50 mm/min. The load (kgf/cm) at the time of peeling 20 mm in the perpendicular direction was measured, and the peeling strength was calculated|required.

<Measurement of thermal conductivity of cured product>

(1) Preparation of samples of cured products

The resin varnish produced in Examples and Comparative Examples was applied on the mold release PET with a die coater so that the thickness of the resin composition layer after drying was 100 μm, and dried at 80° C. to 100° C. (average 90° C.) for 7 minutes to form a resin sheet. was obtained.

Using a batch type vacuum pressurizing laminator (a two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) for the produced resin sheet, three resin composition layers were laminated, and then the resin composition layer was cured at 180° C. for 90 minutes. was cured to obtain a sample. The laminate was pressure-reduced for 30 second, the atmospheric pressure was 13 hPa or more, and the sample of the hardened|cured material was obtained by pressing by 120 degreeC and the pressure of 0.4 Mpa for 20 second after that.

(2) Measurement of thermal diffusivity α

About the sample of hardened|cured material, the thermal diffusivity alpha (m<2>/s) of the said hardened|cured material sample in the thickness direction was measured by the thermal wave analysis method using "ai-Phase Mobile 1u" manufactured by ai-Phase. The same sample was measured 3 times, and the average value was computed.

3) Measurement of specific heat capacity Cp

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

(4) Measurement of density ρ

The density (kg/m3) of the hardened|cured material sample was measured using the METTLER TOLEDO company analytical balance XP105 (using a specific gravity measurement kit).

(5) Calculation of thermal conductivity λ

Substituting the heat diffusivity α (m2/s), specific heat capacity Cp (J/kg·K), and density ρ (kg/m3) obtained in (2) to (4) above into the following formula (I), the thermal conductivity λ (W/m·K) was calculated.

λ=α×Cp×ρ (I)

<Evaluation of Fillability>

The resin varnish was prepared so that the solid content concentration of the resin varnish produced in the Example and the comparative example might be 85 mass % or more, and it apply|coated with the die-coater so that the thickness of the resin composition layer after drying might be set to 100 micrometers on mold release PET. “○” indicates that the resin varnish viscosity exceeded 1.5 Pa·s (25°C, E-type viscometer) and the moldability was poor, and “Δ” indicates that the resin varnish viscosity was exceeds 2.5 Pa·s (25°C, E-type viscometer), and the case where it was not possible to shape|mold into a sheet shape was made into "x".

<Synthesis Example 1: Synthesis of Elastomer 1>

69 g of G-3000 (bifunctional hydroxyl group terminal polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g/eq., solid content 100 mass%: manufactured by Nippon Soda Corporation) in a reaction vessel; 40 g of Ifsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Sekiyu Chemical Co., Ltd.) and 0.005 g of dibutyl tin laurate were mixed and uniformly dissolved. When it became uniform, the temperature was raised to 50°C, and 8 g of isophorone diisocyanate (Evonik Degusa Japan, IPDI isocyanate group equivalent = 113 g/eq.) was added while further stirring, followed by reaction for about 3 hours. Subsequently, the reaction product was cooled to room temperature, and 23 g of cresol novolak resin (KA-1160, manufactured by DIC, hydroxyl equivalent = 117 g/eq.) and 60 g of ethyldiglycol acetate (made by Daicel) were added thereto. , the temperature was raised to 80° C. while stirring, and the reaction was performed for about 4 hours. The disappearance of the 2250 cm ^-1 NCO peak was confirmed from FT-IR. With the confirmation of the disappearance of the NCO peak, it was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a 100-mesh filter cloth to obtain Elastomer 1 (non-volatile content 50% by mass) having a polybutadiene structure and a phenolic hydroxyl group. . The number average molecular weight was 5500.

<Synthesis Example 2: Synthesis of Elastomer 2>

50 g of G-3000 (bifunctional hydroxyl group terminal polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g/eq., solid content: 100 mass%: manufactured by Nippon Soda) in a reaction vessel; 23.5 g of Ifsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Sekiyu Chemical Co., Ltd.) and 0.005 g of dibutyl tin laurate were mixed and uniformly dissolved. When it became uniform, it heated up to 50 degreeC, 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g/eq.) was added, stirring further, and reaction was performed for about 3 hours. Next, after cooling the reaction product to room temperature, 8.96 g of benzophenonetetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g/eq.), 0.07 g of triethylenediamine, and ethyldiglycol acetate (manufactured by Daicel) 40.4 g was added, the temperature was raised to 130°C while stirring, and reaction was performed for about 4 hours. The disappearance of the 2250 cm ^-1 NCO peak was confirmed from FT-IR. With the confirmation of the disappearance of the NCO peak, it was regarded as the end point of the reaction, the reaction product was cooled to room temperature, and then filtered through a 100-mesh filter cloth, and elastomer 2 having an imide structure, a urethane structure, and a polybutadiene structure (non-volatile content 50% by mass) ) was obtained. The number average molecular weight was 13700.

<Measurement of average particle diameter of thermally conductive filler>

To a 20 ml vial bottle, 0.01 g of a thermally conductive filler, 0.2 g of a nonionic dispersant (“T208.5” manufactured by Nippon Yushi Co., Ltd.), and 10 g of pure water were added, followed by ultrasonic dispersion for 10 minutes with an ultrasonic cleaner, the sample was prepared Next, the sample was put into a laser diffraction particle size distribution analyzer ("SALD2200" manufactured by Shimadzu Corporation), and ultrasonic waves were irradiated for 10 minutes while being circulated. Then, the ultrasonic wave was stopped, the particle size distribution was measured while the circulation of the sample was maintained, and the average particle diameter of the thermally conductive filler was calculated|required. In addition, 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 calculated|required by the nitrogen BET method using the automatic specific surface area measuring apparatus ("Macsorb HM-1210" by Muntech Corporation).

<Used thermally conductive filler>

Alumina 1: Alumina from which an average particle diameter and a specific surface area differ was mixed, and it prepared so that it might become an average particle diameter of 4.2 micrometers and a specific surface area of 0.8 m<2>/g.

Alumina 2: Alumina from which an average particle diameter and a specific surface area differ was mixed, and it prepared so that it might become an average particle diameter of 3.0 micrometers and a specific surface area of 1.5 m<2>/g.

Alumina 3: Alumina having an average particle diameter of 4 µm ("CB-P05" manufactured by Showa Denko Corporation, specific surface area of 0.7 m 2 /g)

Alumina 4: Alumina having an average particle diameter of 2 µm ("CB-P02" manufactured by Showa Denko Corporation, specific surface area 1.1 m 2 /g)

<Example 1>

4 parts of highly resilient elastic epoxy resin (“YX7400” manufactured by Mitsubishi Chemical, 440 g/eq of epoxy equivalent), liquid epoxy resin (“ZX1059” manufactured by Nippon-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 (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185 g/eq) 2 parts are dissolved in 10 parts of cyclohexanone , alumina 1 215 parts, elastomer 1 (50 mass% solid content, number average molecular weight 5500) 20 parts, solid naphthol-based curing agent (“SN485” manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution having a solid content of 50%) 6 parts, 3 parts of hardening accelerators (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5 mass %), and 15 parts of methyl ethyl ketone were mixed, it disperse|distributed uniformly with a high-speed rotary mixer, and the resin varnish was produced.

<Example 2>

6 parts of highly resilient elastic epoxy resin (“YX7400” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 440 g/eq), liquid epoxy resin (“ZX1059” manufactured by Nippon-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 (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185 g/eq) 2 parts are dissolved in 10 parts of cyclohexanone , alumina 2 210 parts, elastomer 1 (50 mass% solid content, number average molecular weight 5500) 20 parts, solid naphthol-based curing agent (“SN485” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution having a solid content of 50%) 6 parts, 3 parts of hardening accelerators (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5 mass %), and 15 parts of methyl ethyl ketone were mixed, it disperse|distributed uniformly with a high-speed rotary mixer, and the resin varnish was produced.

<Example 3>

4 parts of highly resilient elastic epoxy resin (“YX7400” manufactured by Mitsubishi Chemical, 440 g/eq of epoxy equivalent), liquid epoxy resin (“ZX1059” manufactured by Nippon-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 (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185 g/eq) 2 parts are dissolved in 10 parts of cyclohexanone , alumina 2 210 parts, elastomer 1 (50 mass% solid content, number average molecular weight 5500) 24 parts, solid naphthol-based curing agent (“SN485” manufactured by Nippon-Sumikin Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution having a solid content of 50%) 6 parts, 3 parts of hardening accelerators (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5 mass %), and 13 parts of methyl ethyl ketone were mixed, it disperse|distributed uniformly with a high-speed rotary mixer, and the resin varnish was produced.

<Example 4>

4 parts of highly resilient elastic epoxy resin (“YX7400” manufactured by Mitsubishi Chemical, 440 g/eq of epoxy equivalent), liquid epoxy resin (“ZX1059” manufactured by Nippon-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 (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185 g/eq) 2 parts are dissolved in 7 parts of cyclohexanone , 170 parts of alumina 2, elastomer 1 (50 mass% solid content, number average molecular weight 5500) 24 parts, solid naphthol-based curing agent (“SN485” manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution having a solid content of 50%) 6 parts, 3 parts of hardening accelerators (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5 mass %), and 9 parts of methyl ethyl ketone were mixed, it disperse|distributed uniformly with a high-speed rotary mixer, and the resin varnish was produced.

<Example 5>

4 parts of highly resilient elastic epoxy resin (“YX7400” manufactured by Mitsubishi Chemical, 440 g/eq of epoxy equivalent), liquid epoxy resin (“ZX1059” manufactured by Nippon-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 (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185 g/eq) 3 parts were dissolved in 13 parts of cyclohexanone , alumina 1 215 parts, elastomer 1 (50 mass% solid content, number average molecular weight 5500) 12 parts, solid naphthol-based curing agent (“SN485” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution having a solid content of 50%) 8 parts, 3 parts of hardening accelerators (4-dimethylaminopyridine (DMAP), MEK solution of 5 mass % of solid content), and 15 parts of methyl ethyl ketone were mixed, it disperse|distributed uniformly with a high-speed rotary mixer, and the resin varnish was produced.

<Example 6>

4 parts of highly resilient elastic epoxy resin (“YX7400” manufactured by Mitsubishi Chemical, 440 g/eq of epoxy equivalent), liquid epoxy resin (“ZX1059” manufactured by Nippon-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 (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185 g/eq) 2 parts are dissolved in 10 parts of cyclohexanone , Alumina 1 215 parts, Elastomer 2 (solid content 50% by mass, number average molecular weight 13700) 20 parts, solid naphthol-based curing agent (“SN485” manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution having a solid content of 50%) 6 parts, 3 parts of hardening accelerators (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5 mass %), and 15 parts of methyl ethyl ketone were mixed, it disperse|distributed uniformly with a high-speed rotary mixer, and the resin varnish was produced.

<Example 7>

4 parts of highly resilient elastic epoxy resin (“YX7400” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 440 g/eq), liquid epoxy resin (“ZX1059” manufactured by Nippon-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 (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185 g/eq) 2 parts are dissolved in 10 parts of cyclohexanone , Alumina 2 210 parts, Elastomer 2 (solid content 50% by mass, number average molecular weight 13700) 24 parts, solid naphthol-based curing agent (“SN485” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution having a solid content of 50%) 6 parts, 3 parts of hardening accelerators (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5 mass %), and 13 parts of methyl ethyl ketone were mixed, it disperse|distributed uniformly with a high-speed rotary mixer, and the resin varnish was produced.

<Comparative Example 1>

4 parts of highly resilient elastic epoxy resin (“YX7400” manufactured by Mitsubishi Chemical, 440 g/eq of epoxy equivalent), liquid epoxy resin (“ZX1059” manufactured by Nippon-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, bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185 g/eq) 3 parts are dissolved in 14 parts of cyclohexanone , alumina 1 215 parts, polyester resin (manufactured by Unichika, UE3400) 5 parts, solid naphthol-based curing agent (“SN485” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution with a solid content of 50%) 10 parts , 3 parts of a curing 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>

4 parts of highly resilient elastic epoxy resin (“YX7400” manufactured by Mitsubishi Chemical, 440 g/eq of epoxy equivalent), liquid epoxy resin (“ZX1059” manufactured by Nippon-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, bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185 g/eq) 3 parts are dissolved in 5 parts of cyclohexanone , 100 parts of alumina 1, polyester resin (manufactured by Unichika, UE3400) 5 parts, solid naphthol-based curing agent (“SN485” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution with a solid content of 50%) 10 parts , 3 parts of a curing 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>

4 parts of highly resilient elastic epoxy resin (“YX7400” manufactured by Mitsubishi Chemical, 440 g/eq of epoxy equivalent), liquid epoxy resin (“ZX1059” manufactured by Nippon-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 (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185 g/eq) 2 parts are dissolved in 10 parts of cyclohexanone , alumina 3 215 parts, elastomer 1 (50 mass% solid content, number average molecular weight 5500) 20 parts, solid naphthol-based curing agent (“SN485” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution having a solid content of 50%) 6 parts, 3 parts of hardening accelerators (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5 mass %), and 15 parts of methyl ethyl ketone were mixed, it disperse|distributed uniformly with a high-speed rotary mixer, and the resin varnish was produced.

<Comparative Example 4>

4 parts of highly resilient elastic epoxy resin (“YX7400” manufactured by Mitsubishi Chemical, 440 g/eq of epoxy equivalent), liquid epoxy resin (“ZX1059” manufactured by Nippon-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 (“YX4000HK” manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent: 185 g/eq) 2 parts are dissolved in 10 parts of cyclohexanone , alumina 4 210 parts, elastomer 1 (50 mass% solid content, number average molecular weight 5500) 24 parts, solid naphthol-based curing agent (“SN485” manufactured by Shin-Nippon Sumikin Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution having a solid content of 50%) 6 parts, 3 parts of hardening accelerators (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5 mass %), and 13 parts of methyl ethyl ketone were mixed, it disperse|distributed uniformly with a high-speed rotation mixer, and the resin varnish was produced.

Abbreviations etc. in the table below are as follows.

Elastomer 1: Elastomer prepared in Synthesis Example 1

Elastomer 2: Elastomer prepared in Synthesis Example 2

YX7400: high repulsion elastic epoxy resin, epoxy equivalent 440 g/eq, manufactured by Mitsubishi Chemical Corporation

ZX1059: 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g/eq, manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd.

YX4000HK: Bixylenol type epoxy resin, epoxy equivalent: 185 g/eq, manufactured by Mitsubishi Chemical Corporation

Alumina 1: A mixture of alumina different in average particle diameter and specific surface area, average particle diameter 4.2 μm, specific surface area 0.8 m 2 /g

Alumina 2: A mixture of alumina different in average particle diameter and specific surface area, average particle diameter 3.0 μm, specific surface area 1.5 m 2 /g

Alumina 3: Alumina having an average particle diameter of 4 µm ("CB-P05" manufactured by Showa Denko Corporation, specific surface area of 0.7 m 2 /g)

Alumina 4: Alumina having an average particle diameter of 2 µm ("CB-P02" manufactured by Showa Denko Corporation, specific surface area 1.1 m 2 /g)

SN485: solid naphthol-based curing agent, hydroxyl equivalent of 215, MEK solution having a solid content of 50%, manufactured by Nippon-Sumikin Chemical Co., Ltd.

DMAP: hardening accelerator, 4-dimethylaminopyridine, MEK solution of 5 mass % of solid content

UE3400: polyester resin, manufactured by Unichika

(A) Content of component: Content (mass %) when the nonvolatile component of the resin composition except (C) component is 100 mass % is shown.

(C) Content of component: Content (mass %) when the nonvolatile component of a resin composition is 100 mass % is shown.

[Table 1]

As shown in Examples 1-7, it turns out that the insulating layer formed from the resin composition containing (A)-(C) component is excellent in thermal conductivity and the peeling strength with respect to a metal layer. Moreover, since Examples 1-7 are excellent in fillability, it also turns out that it is easy to form into a film in a sheet form. On the other hand, it can be seen that Comparative Examples 1 to 2 not including the component (A) have inferior peel strength compared to Examples 1 to 7. Moreover, the comparative examples 3-4 which do not contain (C)component were not able to shape|mold into a sheet form in a viscosity exceeding 2.5 Pa*s, and were not able to evaluate the peeling strength and thermal conductivity. In addition, even when components (D) and (E) are not contained, it is confirmed that the same results as in the above examples are obtained, although there is a difference in the degree.

100 semiconductor chip package
110 semiconductor chip
120 sealing layer
130 Rewiring forming layer (insulating layer)
140 conductor layer (rewiring layer)
150 Solder Resist Layer
160 bump

Claims (18)

(A) a resin having at least one structure selected from a polybutadiene structure, a polysiloxane structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in a molecule;
(B) an epoxy resin having an aromatic structure, and
(C) contains a thermally conductive filler,
(C) the component has an average particle diameter of 2.5 μm to 5.0 μm, and a specific surface area of 0.8 m 2 /g or more,
(A) the component,
has a number average molecular weight (Mn) of 1,000 to 1,000,000, or
At least one selected from a resin having a glass transition temperature of 25° C. or less and a liquid resin at 25° C.,
(A) Resin composition whose content of a component is 10 mass % or more and 65 mass % or less, when a resin component is 100 mass %. The resin composition of Claim 1 whose peeling strength of the metal layer and the hardened|cured material which thermosetted the resin composition at 180 degreeC for 90 minutes is 0.4 kgf/cm or more. The resin composition of Claim 1 whose peeling strength of the hardened|cured material which thermosetted the resin composition at 180 degreeC for 90 minutes, and an electrolytic copper foil is 0.4 kgf/cm or more. The resin composition of Claim 1 whose content of (C)component is 87 mass % or more when the non-volatile component in a resin composition makes 100 mass %. The resin composition according to claim 1, wherein the component (C) is alumina. The resin composition according to claim 1, wherein a cured product obtained by thermosetting the resin composition at 180°C for 90 minutes has a thermal conductivity of 1.5 W/m·K to 5.0 W/m·K. The resin composition according to claim 1, wherein the component (A) has a functional group capable of reacting with the component (B). The resin composition according to claim 1, wherein the component (A) has at least one functional group 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 claim 1, wherein the component (A) has an imide structure. The resin composition according to claim 1, wherein the component (A) has a phenolic hydroxyl group. The resin composition according to claim 1, wherein the component (A) has a polybutadiene structure and a phenolic hydroxyl group. The resin composition according to claim 1, which is a resin composition for an insulating layer of a semiconductor chip package. A resin sheet comprising a support and a resin composition layer formed on the support and comprising the resin composition according to any one of claims 1 to 12. The resin sheet according to claim 13, which is a resin sheet for an insulating layer of a semiconductor chip package. The circuit board containing the insulating layer formed with the hardened|cured material of the resin composition in any one of Claims 1-12. A semiconductor chip package comprising the circuit board according to claim 15 and a semiconductor chip mounted on the circuit board. A semiconductor comprising a semiconductor chip sealed by the resin composition according to any one of claims 1 to 12 or by a resin sheet having a support and a resin composition layer comprising the resin composition formed on the support. chip package.
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