JP2018053092A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of giving an insulating layer which suppresses the occurrence of warpage and is excellent in adhesion to a conductor layer even with low roughness, and to provide a resin sheet, a circuit board, and a semiconductor chip package using the resin composition.SOLUTION: The resin composition contains: (A) a resin having one or more structures selected from a polybutadiene structure, a polysiloxane structure, a (meth)acrylate structure, an alkylene structure, an alkyleneoxy structure, an isoprene structure, an isobutylene structure, and a polycarbonate structure in the molecule; (B) an epoxy resin having an aromatic structure; (C) a carbodiimide compound; (D) a biphenyl aralkyl type resin (excluding ones corresponding to the component (B)); and (E) an inorganic filler.SELECTED DRAWING: None

Description

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

  In recent years, the demand for small, high-performance electronic devices such as smartphones and tablet devices has increased, and with this, semiconductor package insulating materials (insulating layers) used in these small electronic devices are required to have higher functionality. It has been.

  For example, an insulating layer used for a wafer level chip size package or a wiring board having an embedded wiring layer is required to suppress warpage generated when the insulating layer is formed and to have high adhesion to the conductor layer.

  For example, Patent Document 1 discloses a thermosetting resin composition containing a specific linear modified polyimide resin and a thermosetting resin as the thermosetting resin composition.

JP 2006-37083 A

  However, the material described in Patent Document 1 has a limited resin composition design from the viewpoint of compatibility with other resins, and is used for a wafer level chip size package or a wiring board having an embedded wiring layer. The application to the insulating layer is limited.

  The present invention provides a resin composition suitable for forming an insulating layer used for a wafer level chip size package or a wiring board having an embedded wiring layer. Resin composition capable of obtaining an insulating layer excellent in adhesiveness with a conductor layer even when the roughness is low, and a resin sheet, a circuit board, and a semiconductor chip package using the resin composition It is to provide.

  The inventors selected (A) in the molecule from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure. A resin having one or more kinds of structures, (B) an epoxy resin having an aromatic structure, (C) a carbodiimide compound, (D) a biphenyl aralkyl type resin (except for those corresponding to the component (B)), and (E) By containing an inorganic filler, the occurrence of warpage is suppressed, and it is found that an insulating layer having excellent adhesion to a conductor layer can be obtained even with low roughness, and the present invention is completed. It came. Furthermore, it has been found that the insulating layer is excellent in laser via reliability and heat resistance because generation of a resin residue is suppressed when forming the laser via.

That is, the present invention includes the following contents.
[1] (A) One type selected from polybutadiene structure, polysiloxane structure, poly (meth) acrylate structure, polyalkylene structure, polyalkyleneoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure in the molecule A resin having the above structure,
(B) an epoxy resin having an aromatic structure,
(C) a carbodiimide compound,
A resin composition containing (D) a biphenyl aralkyl type resin (excluding those corresponding to the component (B)), and (E) an inorganic filler.
[2] The resin composition according to [1], wherein an elastic modulus at 23 ° C. of a cured product obtained by thermosetting the resin composition at 180 ° C. for 90 minutes is 17 GPa or less.
[3] The content of the component (A) is 30% by mass to 85% by mass when the nonvolatile component of the resin composition excluding the component (E) is 100% by mass, [1] or [2] The resin composition described in 1.
[4] The resin composition according to any one of [1] to [3], wherein the content of the component (E) is 60% by mass or more when the nonvolatile component in the resin composition is 100% by mass. .
[5] The component (A) according to any one of [1] to [4], wherein the component (A) is at least one selected from a resin having a glass transition temperature of 25 ° C. or lower and a resin that is liquid at 25 ° C. Resin composition.
[6] The resin composition according to any one of [1] to [5], wherein the component (A) has a functional group capable of reacting with the component (B).
[7] [1] to [6], wherein the component (A) has one or more functional groups selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. The resin composition in any one.
[8] The resin composition according to any one of [1] to [7], wherein the component (A) has an imide structure.
[9] The resin composition according to any one of [1] to [8], wherein the component (A) has a phenolic hydroxyl group.
[10] The resin composition according to any one of [1] to [9], wherein the component (A) has a polybutadiene structure and has a phenolic hydroxyl group.
[11] The resin composition according to any one of [1] to [10], wherein the component (D) has a maleimide group in the molecule.
[12] The resin composition according to any one of [1] to [11], which is a resin composition for an insulating layer of a semiconductor chip package.
[13] A resin sheet having a support and a resin composition layer including the resin composition according to any one of [1] to [12] provided on the support.
[14] The resin sheet according to [13], which is a resin sheet for an insulating layer of a semiconductor chip package.
[15] A circuit board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [12].
[16] A semiconductor chip package comprising the circuit board according to [15] and a semiconductor chip mounted on the circuit board.
[17] A semiconductor chip package including a semiconductor chip sealed with the resin composition according to any one of [1] to [12] or the resin sheet according to [13].

  According to the present invention, the occurrence of warpage is suppressed, and a resin composition capable of obtaining an insulating layer having excellent adhesion to a conductor layer even with low roughness; a resin sheet using the resin composition, A circuit board and a semiconductor chip package can be provided.

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

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

[Resin composition]
The resin composition of the present invention comprises (A) a molecule having a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure. Resin having one or more selected structures, (B) epoxy resin having aromatic structure, (C) carbodiimide compound, (D) biphenyl aralkyl type resin (except those corresponding to component (B)) And (E) an inorganic filler.

  (A) Component, (B) component, (C) component, (D) component, and (E) component are made to contain in a resin composition, generation | occurrence | production of curvature is suppressed, and it is a conductor layer even if it is low roughness It is possible to obtain an insulating layer that is excellent in adhesion. The resin composition may further contain (F) a curing accelerator, (G) a curing agent, and (H) a flame retardant, if necessary. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) One or more kinds selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule Resin having structure>
The resin composition of the present invention has, as component (A), a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polypolyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate in the molecule. A resin having at least one structure selected from the structures is included. Component (A) is one kind selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule. Flexibility is shown by having the above structure. By including a flexible resin such as the component (A), the insulating layer has a low elastic modulus, and the occurrence of warpage can be suppressed. “(Meth) acrylate” refers to methacrylate and acrylate.

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

As the polyalkylene structure, a polyalkylene structure having 2 to 15 carbon atoms is preferable, a polyalkylene structure having 3 to 10 carbon atoms is more preferable, and a polyalkylene structure having 5 to 6 carbon atoms is more preferable.
As the polyalkyleneoxy structure, a polyalkyleneoxy structure having 2 to 15 carbon atoms is preferable, a polyalkyleneoxy structure having 3 to 10 carbon atoms is more preferable, and a polyalkyleneoxy structure having 5 to 6 carbon atoms is more preferable. .

  The component (A) preferably has a high molecular weight in order to exhibit flexibility, and the number average molecular weight (Mn) is preferably 1,000 to 1,000,000, more preferably 5,000 to 9,00,000. 000. The number average molecular weight (Mn) is a polystyrene equivalent number average molecular weight measured using GPC (gel permeation chromatography).

  In order to show flexibility, the component (A) is preferably at least one resin selected from a resin having a glass transition temperature (Tg) of 25 ° C. or lower and a resin that is liquid at 25 ° C.

  The glass transition temperature of the resin having a glass transition temperature (Tg) of 25 ° C. or lower is preferably 20 ° C. or lower, more preferably 15 ° C. or lower. Although the minimum of a glass transition temperature is not specifically limited, Usually, it can be set as -15 degreeC or more. The resin that is liquid at 25 ° C. is preferably a resin that is liquid at 20 ° C. or lower, more preferably a resin that is liquid at 15 ° C. or lower.

  (A) As a component, it is preferable to have a functional group which can react with the (B) component mentioned later from a viewpoint of improving the mechanical strength of hardened | cured material. In addition, as a functional group which can react with (B) component, the functional group which appears by heating shall also be included.

  In a preferred embodiment, the functional group capable of reacting with the component (B) is selected from the group consisting of a hydroxy group, a carboxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. It is a functional group of more than species. Among these, the functional group is preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, or a urethane group, more preferably a hydroxy group, an acid anhydride group, a phenolic hydroxyl group, or an epoxy group. A functional hydroxyl group is particularly preferred. However, when an epoxy group is included as a functional group, the component (A) does not have an aromatic structure.

  A preferred embodiment of the component (A) is a butadiene resin. The butadiene resin is preferably a butadiene resin that is liquid at 25 ° C. or has a glass transition temperature of 25 ° C. or less, such as a hydrogenated polybutadiene skeleton-containing resin (for example, a hydrogenated polybutadiene skeleton-containing epoxy resin), a hydroxy group-containing butadiene resin, or a phenolic hydroxyl group-containing butadiene. Resin (resin having a polybutadiene structure and having a phenolic hydroxyl group), carboxy group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin, and urethane group-containing butadiene resin One or more resins selected from the group are more preferable, and phenolic hydroxyl group-containing butadiene resins are more preferable. Here, the “butadiene resin” means a resin containing a butadiene structure, and in these resins, the butadiene structure may be contained in the main chain or in the side chain. A part or all of the butadiene structure may be hydrogenated. Here, the “hydrogenated polybutadiene skeleton-containing resin” refers to a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and is not necessarily a resin in which the polybutadiene skeleton is completely hydrogenated.

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

  The functional group equivalent when the butadiene resin has a functional group is preferably 100 to 10,000, and more preferably 200 to 5000. The functional group equivalent is the number of grams of resin containing 1 gram equivalent of functional group. For example, the epoxy group equivalent can be measured according to JIS K7236. 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” (epoxy group-containing polybutadiene), “Ricon 130MA8”, “Ricon 130MA13”, “Ricon 130MA20”, “Ricon 131MA5”, “Ricon 131MA10”, “Ricon 131MA10” manufactured by Clay Valley. “Ricon 131MA17”, “Ricon 131MA20”, “Ricon 184MA6” (anhydride-containing polybutadiene), “JP-100”, “JP-200” (epoxidized polybutadiene), “GQ-1000” (manufactured by Nippon Soda Co., Ltd.) Hydroxyl group, carboxyl group-introduced polybutadiene), "G-1000", "G-2000", "G-3000" (both end hydroxyl group polybutadiene), "GI-1000", "GI-2000", "GI-3000" Hydroxylated polybutadiene at both ends), “PB3600”, “PB4700” (polybutadiene skeleton epoxy resin) manufactured by Daicel, “Epofriend A1005”, “Epofriend A1010”, “Epofriend A1020” (styrene, butadiene and styrene block) Copolymer epoxidized product), “FCA-061L” (hydrogenated polybutadiene skeleton epoxy resin), “R-45EPT” (polybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX Corporation, and the like.

  Further, as another preferred embodiment of the component (A), a resin having an imide structure can also be used. As such component (A), a linear polyimide using a hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride as raw materials (Japanese Patent Laid-Open No. 2006-37083, polyimide described in International Publication No. 2008/153208) Etc. The content of the butadiene structure in the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. Details of the polyimide resin can be referred to the descriptions in JP-A-2006-37083 and International Publication No. 2008/153208, the contents of which are incorporated herein.

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

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

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

  Specific examples of acrylic resins include Teissan resin “SG-70L”, “SG-708-6”, “WS-023”, “SG-700AS”, “SG-280TEA” (carboxy group) manufactured by Nagase ChemteX Corporation. -Containing acrylic ester copolymer resin, acid value 5 to 34 mg KOH / g, weight average molecular weight 400,000 to 900,000, Tg-30 to 5 ° C), "SG-80H", "SG-80H-3", "SG -P3 "(epoxy group-containing acrylate copolymer resin, epoxy equivalent 4761-14285 g / eq, weight average molecular weight 350,000-850,000, Tg 11-12 ° C)," SG-600TEA "," SG-790 "( Hydroxyl group-containing acrylic ester copolymer resin, hydroxyl value 20 to 40 mg KOH / g, weight average molecular weight 500,000 to 1,200,000, Tg-37 to -32 ° C. “ME-2000”, “W-116.3” (carboxy group-containing acrylic ester copolymer resin), “W-197C” (hydroxyl group-containing acrylic ester copolymer resin), “Negami Kogyo Co., Ltd.” KG-25 "," KG-3000 "(epoxy group-containing acrylic ester copolymer resin) and the like.

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

  The number average molecular weight (Mn) and functional group equivalent of the carbonate resin are the same as those of the butadiene resin, and the preferred 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", "C-3090" (polycarbonate diol) manufactured by Kuraray. Etc.

  Further, linear polyimide (PCT / JP2016 / 053609) using a hydroxyl group-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride as raw materials can also be used. The content of the carbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. Details of the polyimide resin can be referred to the description of PCT / JP2016 / 053609, the contents of which are incorporated herein.

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

Specific examples of the polysiloxane resin include “SMP-2006”, “SMP-2003PGMEA”, “SMP-5005PGMEA” manufactured by Shin-Etsu Silicone Co., Ltd., linear polyimide using amine group-terminated polysiloxane and tetrabasic acid anhydride (raw material). International Publication No. 2010/053185).
Specific examples of the alkylene resin include “PTXG-1000” and “PTXG-1800” manufactured by Asahi Kasei Fibers, “YX-7180” (resin containing an alkylene structure having an ether bond) manufactured by Mitsubishi Chemical Corporation, and the like. .
Specific examples of the alkyleneoxy resin include “EXA-4850-150”, “EXA-4816”, “EXA-4822” manufactured by DIC Corporation, “EP-4000”, “EP-4003”, “EP-4010” manufactured by ADEKA, And “EP-4011”, “BEO-60E” and “BPO-20E” manufactured by Shin Nippon Chemical Co., Ltd., “YL7175” and “YL7410” manufactured by Mitsubishi Chemical Corporation.
Specific examples of the isoprene resin include “KL-610” and “KL613” manufactured by Kuraray Co., Ltd.
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.

  Further, preferred embodiments of the further component (A) include acrylic rubber particles, polyamide fine particles, silicone particles and the like. Specific examples of the acrylic rubber particles include resin fine particles obtained by subjecting a resin exhibiting rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber to a chemical crosslinking treatment, insoluble in an organic solvent and infusible, Specifically, XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (manufactured by Gantz Kasei Co., Ltd.), paraloid EXL2655, EXL2602 (manufactured by Kureha Chemical Industries, Ltd.) ) And the like. Specific examples of the polyamide fine particles include aliphatic polyamides such as nylon, and any flexible skeleton such as polyamideimide. Specifically, VESTOSINT 2070 (manufactured by Daicel Huls), SP500 (manufactured by Toray Industries, Inc.) and the like.

  The content of the component (A) in the resin composition is preferably 85% by mass or less when the nonvolatile component of the resin composition excluding the component (E) is 100% by mass from the viewpoint of imparting flexibility. Preferably it is 80 mass% or less, More preferably, it is 75 mass% or less, More preferably, it is 73 mass% or less. Further, the lower limit is preferably 30% by mass or more, more preferably 35% by mass or more, further preferably 45% by mass or more, and still more preferably 55% by mass or more.

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

  Examples of the epoxy resin having an aromatic structure include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, tris Phenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy having aromatic structure Resin, glycidyl ester type epoxy resin having aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic ester having aromatic structure Xy-resin, epoxy resin having butadiene structure having aromatic structure, alicyclic epoxy resin having aromatic structure, heterocyclic epoxy resin, spiro ring-containing epoxy resin having aromatic structure, cyclohexane di having aromatic structure Examples thereof include a methanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin having an aromatic structure, a tetraphenylethane type epoxy resin, and an aminophenol type epoxy resin. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. The component (B) is preferably at least one selected from bisphenol A type epoxy resins, bisphenol F type epoxy resins, aminophenol type epoxy resins, and naphthalene type epoxy resins.

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

  Examples of liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins having an aromatic structure, and glycidyl amine type epoxy resins having an aromatic structure. , Phenol novolac type epoxy resin, alicyclic epoxy resin having ester skeleton having aromatic structure, cyclohexanedimethanol type epoxy resin having aromatic structure, aminophenol type epoxy resin and epoxy having butadiene structure having aromatic structure Resin is preferable, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, aminophenol type epoxy resin and naphthalene type epoxy resin are more. Preferred, bisphenol A type epoxy resin, bisphenol F type epoxy resin, more preferably aminophenol type epoxy resin. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC, “828US”, “jER828EL” (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation. "JER806", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "(Mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin)," EX-721 "(glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation," Celoxide 2021P "manufactured by Daicel Corporation (having an ester skeleton) Alicyclic Epoxy resin), "ZX1658" of Nippon Steel Chemical Co., Ltd., "ZX1658GS" (liquid 1,4 glycidyl cyclohexane) and the like. These may be used alone or in combination of two or more.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin having an aromatic structure, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, 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, naphthy A renether type epoxy resin is more preferable, and a naphthalene type tetrafunctional epoxy resin and a naphthylene ether type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” (manufactured by DIC) Cresol novolac type epoxy resin), “N-695” (cresol novolac type epoxy resin), “HP-7200”, “HP-7200L”, “HP-7200HH”, “HP-7200H”, “HP-7200HHH” ( Dicyclopentadiene type epoxy resin), “EXA7311”, “EXA7311-G3”, “EXA7311-G4”, “EXA7311-G4S”, “HP6000” (naphthylene ether type epoxy resin), “EPPN” manufactured by Nippon Kayaku Co., Ltd. -502H "(trisphenol type epoxy resin)," NC70 0L "(naphthol novolac type epoxy resin)," NC3000H "," NC3000 "," NC3000L "," NC3100 "(biphenyl type epoxy resin)," ESN475V "(naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.," ESN485 "(Naphthol novolac type epoxy resin)," YX4000H "," YL6121 "(biphenyl type epoxy resin)," YX4000HK "(bixylenol type epoxy resin)," YL7760 "(bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YX8800” (anthracene type epoxy resin), “PG-100”, “CG-500” manufactured by Osaka Gas Chemical Co., Ltd., “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., “jER1010 manufactured by Mitsubishi Chemical Corporation " Bisphenol A type epoxy resin), “jER1031S” (tetraphenylethane type epoxy resin), “157S70” (bisphenol novolac type epoxy resin), “YX4000HK” (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YX8800” (Anthracene type epoxy resin), “PG-100”, “CG-500” manufactured by Osaka Gas Chemical Co., Ltd., “YL7800” (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., “jER1031S” manufactured by Mitsubishi Chemical Corporation (Tetra) Phenylethane type epoxy resin). These may be used alone or in combination of two or more.

  (B) As a component, when using together a liquid epoxy resin and a solid epoxy resin, those quantity ratios (solid epoxy resin: liquid epoxy resin) are 1: 0.1-1: 15 by mass ratio. A range is preferred. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) when used in the form of a resin sheet Sufficient flexibility can be obtained, handling properties can be improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the mass ratio of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin: liquid epoxy resin) is in the range of 1: 0.3 to 1:10. Is more preferable, and the range of 1: 0.6 to 1: 8 is even more preferable.

  The content of the epoxy resin having an aromatic structure in the resin composition is preferably from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability when the nonvolatile component in the resin composition is 100% by mass. 1 mass% or more, More preferably, it is 2 mass% or more, More preferably, it is 3 mass% or more. The upper limit of the content of the epoxy resin having an aromatic structure is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass. It is as follows.

  In addition, the content of the epoxy resin having an aromatic structure in the resin composition is the non-volatile component of the resin composition excluding the component (E) from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. When it is 100 mass%, it is 1 mass% or more, More preferably, it is 2 mass% or more, More preferably, it is 3 mass% or more. The upper limit of the content of the epoxy resin having an aromatic structure is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass. It is as follows.

  The epoxy equivalent of the epoxy resin having an aromatic structure is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The weight average molecular weight of the epoxy resin having an aromatic structure is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

<(C) Carbodiimide compound>
The resin composition of the present invention contains a carbodiimide compound as the component (C). A carbodiimide compound is a compound having one or more carbodiimide groups (—N═C═N—) in one molecule, and by providing a component (C), an insulating layer having excellent adhesion to a conductor layer is provided. In particular, when used in combination with the component (D) described later, an insulating layer excellent in heat resistance, laser via reliability, and adhesion to the conductor layer can be provided. As the carbodiimide compound, a compound having two or more carbodiimide groups in one molecule is preferable. A carbodiimide compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  In one embodiment, the carbodiimide compound contained in the resin composition of the present invention contains a structure represented by the following formula (1).

（式中、Ｘは、アルキレン基、シクロアルキレン基又はアリーレン基を表し、これらは置換基を有していてもよい。ｐは１〜５の整数を表す。Ｘが複数存在する場合、それらは同一でも相異なってもよい。＊は結合手を表す。）

(In the formula, X represents an alkylene group, a cycloalkylene group or an arylene group, which may have a substituent. P represents an integer of 1 to 5. When a plurality of Xs are present, they are (It may be the same or different. * Represents a bond.)

  The number of carbon atoms of the alkylene group represented by X is preferably 1-20, more preferably 1-10, still more preferably 1-6, 1-4, or 1-3. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Preferable examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.

  The number of carbon atoms of the cycloalkylene group represented by X is preferably 3-20, more preferably 3-12, and even more preferably 3-6. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Preferable examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

  The arylene group represented by X is a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon. The number of carbon atoms of the arylene group is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and still more preferably 6 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Preferable examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

  In combination with the component (D), X is preferably an alkylene group or a cycloalkylene group from the viewpoint of realizing an insulating layer that is more excellent in heat resistance, laser via reliability, and adhesion to the conductor layer. These may have a substituent.

The alkylene group, cycloalkylene group or aryl group represented by X may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group, and an acyloxy group. As a halogen atom used as a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. The alkyl group and alkoxy group used as a substituent may be either linear or branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 1. 6, 1-4, or 1-3. The number of carbon atoms of the cycloalkyl group and cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 6. The aryl group used as a substituent is a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon, and the number of carbon atoms is preferably 6 to 24, more preferably 6 to 18, and still more preferably. Is 6-14, even more preferably 6-10. The number of carbon atoms of the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. Acyl group used as a substituent of the formula: -C (= O) group (wherein, ^{R 1} represents an alkyl group or an aryl group.) Represented by -R ¹ refers. The alkyl group represented by R ¹ may be linear or branched, and the number of carbon atoms thereof is preferably 1-20, more preferably 1-10, still more preferably 1-6, It is 1-4 or 1-3. The number of carbon atoms of the aryl group represented by R ¹ is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and even more preferably 6 to 10. The acyloxy group used as a substituent refers to a group represented by the formula: —O—C (═O) —R ¹ (wherein R ¹ has the same meaning as described above). Especially, as a substituent, an alkyl group, an alkoxy group, and an acyloxy group are preferable, and an alkyl group is more preferable.

  In formula (1), p represents an integer of 1 to 5. In combination with the components (A) to (B) and (D), from the viewpoint of realizing an insulating layer that is more excellent in heat resistance, laser via reliability, and adhesion to the conductor layer, p is preferably 1 to 1 4, more preferably 2 to 4, still more preferably 2 or 3.

  In Formula (1), when there are a plurality of X, they may be the same or different. In one preferred embodiment, at least one X is an alkylene group or a cycloalkylene group, and these may have a substituent.

  In a preferred embodiment, the carbodiimide compound is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, when the mass of the entire carbodiimide compound is 100% by mass. More preferably, it contains the structure represented by the formula (1) at 80% by mass or more or 90% by mass or more. The carbodiimide compound may consist essentially of the structure represented by the formula (1) except for the terminal structure. Although it does not specifically limit as a terminal structure of a carbodiimide compound, For example, an alkyl group, a cycloalkyl group, and an aryl group are mentioned, These may have a substituent. The alkyl group, cycloalkyl group, and aryl group used as the terminal structure may be the same as the alkyl group, cycloalkyl group, and aryl group described for the substituent that the group represented by X may have. In addition, the substituent that the group used as the terminal structure may have may be the same as the substituent that the group represented by X may have.

  From the viewpoint of suppressing the generation of outgas when curing the resin composition, the weight average molecular weight of the carbodiimide compound is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, still more preferably 800 or more, Especially preferably, it is 900 or more or 1000 or more. From the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the carbodiimide compound is preferably 5000 or less, more preferably 4500 or less, still more preferably 4000 or less, even more preferably 3500 or less, and particularly preferably 3000 or less. It is. The weight average molecular weight of the carbodiimide compound can be measured by, for example, a gel permeation chromatography (GPC) method (polystyrene conversion).

  In addition, the carbodiimide compound may be derived from the production method and may contain an isocyanate group (—N═C═O) in the molecule. From the viewpoint of obtaining a resin composition exhibiting good storage stability, and in view of realizing an insulating layer exhibiting desired properties, the content of isocyanate groups in the carbodiimide compound (also referred to as “NCO content”) is as follows. Preferably it is 5 mass% or less, More preferably, it is 4 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 2 mass% or less, Most preferably, it is 1 mass% or less, or 0.5 mass% or less.

  A commercially available product may be used as the carbodiimide compound. Examples of commercially available carbodiimide compounds include, for example, Carbodilite (registered trademark) V-02B, V-03, V-04K, V-07 and V-09 manufactured by Nisshinbo Chemical Co., Stabakuzol (registered trademark) P manufactured by Rhein Chemie, P400 and Hykazil 510 are mentioned.

  The content of the component (C) is non-volatile in the resin composition excluding the component (E) from the viewpoint of obtaining an insulating layer excellent in any of heat resistance, laser via reliability, and adhesion to the conductor layer. When the component is 100% by mass, 0.1% by mass or more is preferable, 0.3% by mass or more is more preferable, and 0.5% by mass or more is more preferable. Although the upper limit of content of a carbodiimide compound is not specifically limited, 10 mass% or less is preferable, 8 mass% or less is more preferable, and 5 mass% or less is further more preferable.

<(D) Biphenyl aralkyl type resin (excluding those corresponding to component (B))>
The resin composition of this invention contains biphenyl aralkyl type resin (however, except the thing applicable to (B) component) as (D) component. By including the component (D), it is possible to provide an insulating layer having excellent adhesion to the conductor layer. In particular, when used in combination with the component (C), the heat resistance, laser via reliability, and the conductor layer An insulating layer having excellent adhesion can be provided. In general, the biphenyl aralkyl resin has a low miscibility with a flexible resin and tends to have a low compatibility, but exhibits a particularly good compatibility with the component (A) described above.

（式中、Ｒ^１は、それぞれ独立に水素原子、炭素原子数１〜５のアルキル基、又はフェニル基を表し、Ｒ^２は、それぞれ独立にマレイミド基、シアネート基、又はアミノ基を表し、ｎは平均値であり１＜ｎ≦５を表し、ｍはそれぞれ独立に１〜５の整数を表す。） The component (D) is not particularly limited as long as it has a biphenyl aralkyl structure having no epoxy group, but is preferably a resin represented by the following formula (2).

(In the formula, each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group; each R ² independently represents a maleimide group, a cyanate group, or an amino group; Is an average value and represents 1 <n ≦ 5, and each m independently represents an integer of 1 to 5.)

R ¹ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

  The alkyl group having 1 to 5 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably a methyl group. The alkyl group having 1 to 5 carbon atoms may be linear, branched or cyclic, but is preferably a linear alkyl group. Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, sec-butyl group, and n-pentyl group. It is done.

Among these, it is preferable that R ¹ represents a hydrogen atom, a methyl group, or a phenyl group from the viewpoint of providing an insulating layer having excellent adhesion to the conductor layer.

R ² each independently represents a maleimide group, a cyanate group, or an amide group, and more preferably has a maleimide group from the viewpoint of providing an insulating layer excellent in adhesion to the conductor layer.

  m represents the integer of 1-5 each independently. m preferably represents an integer of 1 to 4, more preferably represents an integer of 1 to 3, and still more preferably represents 1.

  n is an average value and represents 1 <n ≦ 5. When n is 5 or less, the solvent solubility is good. n can be calculated from the value of the weight average molecular weight of the resin represented by the formula (2).

（式中、Ｒ^１及びｎは、式（２）中のものと同じでよい。） The resin represented by the formula (2) is preferably a resin represented by the following formula (3).

(In the formula, R ¹ and n may be the same as those in formula (2).)

  (D) A commercial item may be used for a component. Examples of the commercially available component (D) include MIR-3000 and MIR-3000-70T manufactured by Nippon Kayaku Co., Ltd.

  The content of the component (D) is non-volatile in the resin composition excluding the component (E) from the viewpoint of obtaining an insulating layer excellent in any of heat resistance, laser via reliability, and adhesion to the conductor layer. When the component is 100% by mass, 0.3% by mass or more is preferable, 0.5% by mass or more is more preferable, and 1% by mass or more is more preferable. Although the upper limit of content of (D) component is not specifically limited, 25 mass% or less is preferable, 20 mass% or less is more preferable, and 15 mass% or less is further more preferable.

<(E) Inorganic filler>
The resin composition includes (E) an inorganic filler. The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. As 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 size of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, and even more preferably 2.2 μm or less, from the viewpoint of improving the circuit embedding property and obtaining an insulating layer having a low surface roughness. Preferably it is 2 micrometers or less. Although the minimum of this 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. Examples of commercially available inorganic fillers having such an average particle diameter include, for example, “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C” manufactured by Admatechs, and “UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd. "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama Corporation, "SC2500SQ", "SO-C6", "SO-C4", "SO-C2" manufactured by Admatechs And “SO-C1”.

  The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring apparatus, “LA-500” manufactured by Horiba, Ltd. can be used.

  Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanates from the viewpoint of improving moisture resistance and dispersibility. It is preferable to treat with one or more surface treatment agents such as a system coupling agent. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu. “KBE903” (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  From the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion, the content of the inorganic filler in the resin composition is preferably 60% by mass or more, more preferably, when the nonvolatile component in the resin composition is 100% by mass. It is 70 mass% or more, More preferably, it is 75 mass% or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less from the viewpoint of mechanical strength of the insulating layer, particularly elongation.

<(F) Curing accelerator>
The resin composition may contain (F) a curing accelerator. Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like. A curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing 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 phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

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

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-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'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl Examples include imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2- Phenylimidazole is preferred.

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine 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] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

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

  When the resin composition contains the component (F), the content of the curing accelerator in the resin composition is not particularly limited, but 0.01 mass when the total nonvolatile components in the resin composition is 100 mass%. % To 3% by mass is preferable, 0.03 to 1.5% by mass is more preferable, and 0.05 to 1% by mass is more preferable.

<(G) Curing agent>
The resin composition may contain (G) 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). For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, and a cyanate. Examples include ester-based curing agents. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together. The component (G) is preferably at least one selected from a phenolic curing agent, a naphthol curing agent, an active ester curing agent, and a cyanate ester curing agent, a phenol curing agent, and an active ester curing It is preferable that it is 1 or more types selected from an agent.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type 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 conductor layer.

  Specific examples of the phenol-based curing agent and naphthol-based curing agent include “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., “NHN”, “CBN” manufactured by Nippon Kayaku Co., Ltd. ”,“ GPH ”,“ SN170 ”,“ SN180 ”,“ SN190 ”,“ SN475 ”,“ SN485 ”,“ SN495V ”,“ SN375 ”,“ SN395 ”manufactured by Nippon Steel & Sumitomo Metal,“ TD- ”manufactured by DIC 2090 "," LA-7052 "," LA-7054 "," LA-1356 "," LA-3018-50P "," EXB-9500 "," HPC-9500 "," KA-1160 "," KA- " 1163 "," KA-1165 "," GDP-6115L "," GDP-6115H "manufactured by Gunei Chemical Co., Ltd., and the like.

  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 ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic 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 and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with 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 a phenol novolac, and an active ester compound containing a benzoylated product of a phenol novolac are preferred, Of these, active ester compounds having a naphthalene structure and active ester compounds having a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.

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

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd. and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  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. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolac polyfunctional cyanate ester resins), “BA230”, “BA230S75” (part of bisphenol A dicyanate) manufactured by Lonza Japan. Or a prepolymer which is all triazine-modified into a trimer).

  When the resin composition contains the component (G), the content of the curing agent in the resin composition is not particularly limited, but preferably 10% by mass or less when the nonvolatile component in the resin composition is 100% by mass. More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less. The lower limit is not particularly limited but is preferably 1% by mass or more.

<(H) Flame retardant>
The resin composition may contain (H) 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.

  Commercially available products may be used as the flame retardant, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd.

  When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but preferably 0.5% by mass to 20% by mass when the nonvolatile component in the resin composition is 100% by mass. Preferably 0.5 mass%-15 mass%, More preferably, 0.5 mass%-10 mass% are further more preferable.

<(I) Optional additive>
The resin composition may further contain other additives as necessary. Examples of such other additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, In addition, binders, thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and resin additives such as colorants can be used.

<Physical properties of resin composition>
The cured product obtained by thermally curing the resin composition of the present invention at 180 ° C. for 90 minutes preferably has an elastic modulus at 23 ° C. of 17 GPa or less in order to suppress warpage, and is 16 GPa or less, 15 GPa or less, 14 GPa. Or less, or more preferably 13 GPa or less. Although it does not specifically limit about a minimum, For example, it can be set to 5 GPa or more, 6 GPa or more, 7 GPa or more, etc. By setting the elastic modulus to 17 GPa or less, it is possible to obtain an insulating layer in which the occurrence of warpage of the cured product is suppressed. The elastic modulus can be measured according to the method described later in <Measurement of Elastic Modulus and Measurement of 1% Weight Loss Temperature>.

  A cured product obtained by thermosetting the resin composition of the present invention at 180 ° C. for 30 minutes exhibits excellent adhesion to the conductor layer, that is, excellent peel strength (peel strength) from the conductor layer. The peel strength is preferably 0.4 kgf / cm or more, more preferably 0.45 kgf / cm or more, and further preferably 0.5 kgf / cm or more. On the other hand, the upper limit value of the peel strength is not particularly limited, but may be 1.5 kgf / cm or less, 1 kgf / cm or less, or the like. Evaluation of adhesiveness with a conductor layer can be measured according to the method described in <Measurement and evaluation of peel strength with conductor layer> described later.

  The cured product obtained by thermosetting the resin composition of the present invention at 180 ° C. for 90 minutes exhibits the property that the 1% weight loss temperature is 350 ° C. or higher, and thus exhibits excellent heat resistance. The 1% weight loss temperature is preferably 350 ° C. or higher, more preferably 355 ° C. or higher, and still more preferably 360 ° C. or higher. The upper limit of the 1% weight loss temperature is not particularly limited, but may be 500 ° C. or less. The 1% weight loss temperature can be evaluated according to the method described in <Measurement of Elastic Modulus and Measurement of 1% Weight Loss Temperature> described later.

  When a via hole is formed in a cured product obtained by thermosetting the resin composition of the present invention at 180 ° C. for 30 minutes, the cured product has a short residue length (smear length) at the bottom of the via hole. The smear length is preferably less than 3 μm, more preferably 2.5 μm or less, and further preferably 2 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more.

The resin composition of the present invention can suppress the occurrence of warping, can provide an insulating layer excellent in heat resistance and adhesion to the conductor layer, and also contains components (B) to (D) (A ) Good compatibility of components. Therefore, the resin composition of the present invention forms a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer of a semiconductor chip package) and an insulating layer of a circuit board (including a printed wiring board). Resin composition for forming an interlayer insulating layer that can be suitably used as a resin composition (resin composition for an insulating layer of a circuit board) and on which a conductor layer is formed by plating Can be more suitably used as a resin composition for an interlayer insulating layer of a circuit board on which a conductor layer is formed.
Also suitable as a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip) and a resin composition for forming wiring on a semiconductor chip (resin composition for forming a semiconductor chip wiring) Can be used.

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

  The thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, further preferably 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, or 40 μm or less from the viewpoint of thinning. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 5 micrometers or more, 10 micrometers or more, etc.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly 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, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.

  The support may be subjected to mat treatment or corona treatment on the surface to be bonded to the resin composition layer.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1”, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. “AL-5”, “AL-7”, “Lumirror T60” manufactured by Toray Industries, Inc., “Purex” manufactured by Teijin Limited, “Unipeel” manufactured by Unitika, and the like.

  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. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

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

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol, etc. Carbitols, aromatic hydrocarbons such as toluene and xylene, 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.

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

  In the resin sheet, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The resin sheet can be stored in a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

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

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of thinning, the thickness of the sheet-like fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and even more preferably 600 μm or less. Although the minimum of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it may be 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more, etc.

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

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

  The resin sheet of the present invention can be suitably used for forming an insulating layer in the manufacture of a semiconductor chip package (insulating resin sheet for a semiconductor chip package). For example, the resin sheet of the present invention can be suitably used for forming an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board), and an interlayer insulation on which a conductor layer is formed by plating. In order to form a layer (for an interlayer insulating layer of a circuit board on which a conductor layer is formed by plating), it can be more suitably used. Examples of a 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 (semiconductor chip sealing resin sheet) or forming a wiring on a semiconductor chip (semiconductor chip wiring forming resin sheet). For example, it can be suitably used for Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), Fan-in type PLP, and the like. 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.
The resin sheet of the present invention can also be suitably used for forming a wide range of other applications requiring high insulation reliability, for example, an insulating layer of a circuit board such as a printed wiring board.

[Circuit board]
The circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.
The method for manufacturing the circuit board of the present invention includes:
(1) preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate;
(2) The step of laminating the resin sheet of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer and thermally curing to form an insulating layer;
(3) including a step of interconnecting the wiring layers. 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 the wiring layers can be connected to each other, but a step of forming a via hole in the insulating layer to form the wiring layer, and a step of polishing or grinding the insulating layer to expose the wiring layer It is preferable that it is at least one of these steps.

<Step (1)>
Step (1) is a step of preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate. Usually, the base material with a wiring layer has a first metal layer and a second metal layer which are part of the base material on both surfaces of the base material, respectively, and is opposite to the base material side surface of the second metal layer. A wiring layer is provided on the surface. In detail, a dry film (photosensitive resist film) is laminated on a substrate, and a pattern dry film is formed by exposing and developing under a predetermined condition using a photomask. A wiring layer is formed by electrolytic plating using the developed pattern dry film as a plating mask, and then the pattern dry film is peeled off. Note that the first metal layer and the second metal layer may not be provided.

  Examples of the base material include glass epoxy substrates, metal substrates (such as stainless steel and cold rolled steel plate (SPCC)), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. A metal layer such as a copper foil may be formed on the surface. Further, even if a metal layer such as a peelable first metal layer and a second metal layer (for example, an ultrathin copper foil with a carrier copper foil manufactured by Mitsui Kinzoku Co., Ltd., trade name “Micro Thin”) is formed on the surface. Good.

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

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

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

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

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

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

  The thickness of the wiring layer is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 to 20 μm, or 15 μm, although it depends on the desired wiring board design. In the step (3), when the step of polishing or grinding the insulating layer and exposing the wiring layer to connect the wiring layers to each other is adopted, it is preferable that the wiring of the interlayer connection and the wiring not to be connected are different. . The thickness of the wiring layer can be adjusted by repeating the pattern formation described above. Of each wiring layer, the thickness of the thickest wiring layer (conductive pillar) is preferably 100 μm or less and 2 μm or more, although it depends on the desired wiring board design. Further, the wiring for interlayer connection may be convex.

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

<Step (2)>
Step (2) is a step of laminating the resin sheet of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer, and thermosetting to form an insulating layer. For details, the wiring layer of the substrate with a wiring layer obtained in the above-mentioned step (1) is laminated so as to be embedded in the resin composition layer of the resin sheet, and the resin composition layer of the resin sheet is thermally cured to be insulated. Form a layer.

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

  Lamination of the wiring layer and the resin sheet may be performed by a vacuum laminating method after removing the protective film of the resin sheet. In the vacuum laminating 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 bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 13 hPa or less.

  After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

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

  The support for the resin sheet may be peeled after the resin sheet is laminated on the substrate with the wiring layer and thermally cured, or the support may be peeled off before the resin sheet is laminated on the substrate with the wiring layer. Good. Moreover, you may peel a support body before the roughening process process mentioned later.

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

  The surface roughness (Ra1) of the surface of the insulating layer after polishing is preferably 100 nm or more, more preferably 110 nm or more, and further preferably 120 nm or more. The upper limit is preferably 450 nm or less, more preferably 400 nm or less, and still more preferably 350 nm or less. The surface roughness (Ra1) of the surface of the insulating layer after polishing is described below <surface roughness (Ra1) of the surface of the insulating layer after polishing and cutting, and the maximum cross-sectional height of the roughness curve of the surface of the insulating layer after polishing and cutting. (Rt1), surface roughness (Ra2) of the surface of the insulating layer after the roughening treatment, and measurement of the maximum cross-sectional height (Rt2) of the roughness curve after the roughening treatment> .

  The maximum cross-sectional height (Rt1) of the roughness curve of the insulating layer surface after polishing is preferably 3000 nm or more, more preferably 3500 nm or more, and further preferably 4000 nm or more. An upper limit becomes like this. Preferably it is 7000 nm or less, More preferably, it is 6500 nm or less, More preferably, it is 6000 nm or less. The maximum cross-sectional height (Rt1) of the roughness curve of the insulating layer surface after polishing is described below <surface roughness of the insulating layer surface after polishing cutting (Ra1), and roughness curve of the insulating layer surface after polishing cutting. Measurement of the maximum cross-sectional height (Rt1), the surface roughness (Ra2) of the surface of the insulating layer after the roughening treatment, and the maximum cross-sectional height (Rt2) of the roughness curve after the roughening treatment> Can be measured.

<Step (3)>
Step (3) is a step of interconnecting the wiring layers. More specifically, this is a step of forming via holes in the insulating layer, forming a conductor layer, and interconnecting the wiring layers. Alternatively, the insulating layer is polished or ground, and the wiring layer is exposed to connect the wiring layers.

  When adopting a process of forming a via hole in the insulating layer, forming a conductor layer and interconnecting the wiring layers, the formation of the via hole is not particularly limited, but laser irradiation, etching, mechanical drilling, etc. can be mentioned, but laser irradiation Is preferably carried out by This 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. Specifically, laser irradiation is performed from the surface side of the support of the resin sheet to form a via hole that exposes the wiring layer through the support and the insulating layer.

  The 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.

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

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

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

  The surface roughness (Ra2) of the insulating layer surface after the roughening treatment is preferably 350 nm or more, more preferably 400 nm or more, and further preferably 450 nm or more. The upper limit is preferably 700 nm or less, more preferably 650 nm or less, and still more preferably 600 nm or less. The surface roughness (Ra2) of the insulating layer surface after the polishing is described below <surface roughness of the insulating layer surface after polishing cutting (Ra1), and the maximum cross-sectional height of the roughness curve of the insulating layer surface after polishing cutting. (Rt1), surface roughness (Ra2) of the surface of the insulating layer after the roughening treatment, and measurement of the maximum cross-sectional height (Rt2) of the roughness curve after the roughening treatment> .

  The maximum cross-sectional height (Rt2) of the roughness curve after the roughening treatment is preferably 7000 nm or more, more preferably 7500 nm or more, and further preferably 8000 nm or more. An upper limit becomes like this. Preferably it is 12000 nm or less, More preferably, it is 11000 nm or less, More preferably, it is 10000 nm or less. The maximum cross-sectional height (Rt2) of the roughness curve of the insulating layer surface after polishing is described below <surface roughness of the insulating layer surface after polishing cutting (Ra1), and roughness curve of the insulating layer surface after polishing cutting. Measurement of the maximum cross-sectional height (Rt1), the surface roughness (Ra2) of the surface of the insulating layer after the roughening treatment, and the maximum cross-sectional height (Rt2) of the roughness curve after the roughening treatment> Can be measured.

  After forming the via hole, a conductor layer is formed. The conductor material which comprises a conductor layer is not specifically limited, A conductor layer can be formed by arbitrary well-known methods, such as plating, a sputter | spatter, vapor deposition, and it is preferable to form by plating. In a preferred embodiment, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. 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 multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated.

  Specifically, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. An electrolytic plating layer is formed on the exposed plating seed layer by electrolytic plating. At that time, the filled via may be formed by filling the via hole by electrolytic plating together with the formation of the electrolytic plating layer. After the electrolytic plating layer is formed, the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be 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 the said dry film.

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

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

  When adopting a process of polishing or grinding the insulating layer and exposing the wiring layer to connect the wiring layers, the insulating layer polishing method or grinding method can be used to expose the wiring layer, polishing or grinding surface If it is horizontal, it will not specifically limit, A conventionally well-known grinding | polishing method or grinding method can be applied, for example, the chemical mechanical polishing method by a chemical mechanical polishing apparatus, the mechanical polishing methods, such as a buff, The surface grinding method by grindstone rotation Etc. Similar to the step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers to each other, a smear removing step and a roughening step may be performed, or a conductor layer may be formed. Further, it is not necessary to expose all the wiring layers, and a part of the wiring layers may be exposed.

<Process (4)>
Step (4) is a step of removing the base material and forming the circuit board of the present invention. The method for removing the substrate is not particularly limited. In a preferred 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. As needed, you may peel a base material 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 present invention.

  As long as the terminal electrode of the semiconductor chip is conductively connected to the circuit wiring of the circuit board, the joining condition is not particularly limited, and a known condition used in flip chip mounting of the semiconductor chip may be used. Further, the semiconductor chip and the circuit board may be joined via an insulating adhesive.

  In a preferred embodiment, the semiconductor chip is pressure-bonded 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 seconds. (Preferably 5 to 30 seconds).

  In another preferred embodiment, the semiconductor chip is reflowed and bonded to the circuit board. As reflow conditions, it can be set as the range of 120 to 300 degreeC, for example.

  After the semiconductor chip is bonded to the circuit board, for example, the semiconductor chip package can be obtained by filling the semiconductor chip with a mold underfill material. The method of filling with the mold underfill material can be performed by a known method. The resin composition or resin sheet of the present invention can also be used as a mold underfill material.

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

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

  The material used for the substrate is not particularly limited. As a base material, a silicon wafer; a glass wafer; a glass substrate; a metal substrate such as copper, titanium, stainless steel, cold rolled steel plate (SPCC); a substrate subjected to thermosetting treatment by impregnating glass fiber with an epoxy resin or the like (for example, FR- 4 substrate); a substrate made of bismaleimide triazine resin (BT resin), and the like.

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

<Process (B)>
Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. The semiconductor chip can be temporarily fixed using a known apparatus such as a flip chip bonder or a die bonder. The layout and the number of semiconductor chips can be appropriately set according to the shape and size of the temporarily fixed film, the number of target semiconductor packages produced, and the like, for example, a matrix having a plurality of rows and a plurality of columns. Can be aligned and fixed temporarily.

<Process (C)>
Step (C) is a step of laminating the resin composition layer of the resin sheet of the invention on a semiconductor chip, or applying the resin composition of the invention on a semiconductor chip and thermally curing to form a sealing layer. is there. In the step (C), it is preferable that the resin composition layer of the resin sheet of the present invention is laminated on a semiconductor chip and thermally cured to form a sealing layer.

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

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

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

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

<Process (D)>
A process (D) is a process of peeling a base material and a temporary fixing film from a semiconductor chip. The method of peeling can be appropriately changed according to the material of the temporarily fixed film, for example, the method of heating, foaming (or expanding) the temporarily fixed film and peeling, and irradiating ultraviolet rays from the substrate side, Examples include a method of reducing the pressure-sensitive adhesive strength of the temporarily fixed film and peeling it off.

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

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

  The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties at the time of forming the rewiring forming layer (insulating layer). From the viewpoint of ease of manufacturing the semiconductor chip package, Photosensitive resins and thermosetting resins are preferred. 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 forming the rewiring layer (insulating layer), via holes may be formed in the rewiring layer (insulating layer) in order to connect the semiconductor chip and a conductor layer described later.

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

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

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

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

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

  The 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.

  The shape of the via hole, that is, the shape of the outline of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole (the diameter of the opening on the surface of the rewiring layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. Although a minimum 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)>
Step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer). The method for forming the conductor layer on the rewiring layer (insulating layer) is the same as the method for forming the conductor layer after forming the via hole in the insulating layer in the step (3) in the method for manufacturing a circuit board, and is preferable. The range is the same. Note that the step (E) and the step (F) may be repeated, and the conductor layer (redistribution layer) and the redistribution formation layer (insulating layer) may be alternately stacked (build-up).

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

  The material for forming the solder resist layer is not particularly limited as long as it has insulating properties at the time of forming the solder resist layer. From the viewpoint of ease of manufacturing a semiconductor chip package, a photosensitive resin and a 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.

  Further, in the step (G), a bumping process for forming bumps may be performed as necessary. The bumping process can be performed by a known method such as solder ball or solder plating. The via hole can be formed in the bumping process in the same manner as in the step (E).

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

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

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

[Semiconductor device]
Semiconductor devices to be mounted with the semiconductor chip package of the present invention include electrical products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles ( For example, various semiconductor devices used for motorcycles, automobiles, trains, ships, airplanes, and the like) can be given.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

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

(2) Lamination of resin sheet PET film ("Lumirror R80" manufactured by Toray Industries, Inc.) obtained by releasing the resin varnish produced in Examples and Comparative Examples with an alkyd resin release agent ("AL-5" manufactured by Lintec) The resin composition layer after drying is applied with a die coater so that the thickness of the resin composition layer after drying is 200 μm on a thickness of 38 μm, a softening point of 130 ° C., and hereinafter referred to as “release PET”. The resin sheet was obtained by drying at (average 100 ° C.) for 10 minutes. This resin sheet was laminated using a batch-type vacuum pressure laminator (MVLP-500, manufactured by Meiki Co., Ltd.) so that the resin composition layer was in contact with both surfaces of the inner circuit board. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of resin composition layer Release PET was peeled from the laminated resin sheet, and the resin composition layer was cured under curing conditions at 180 ° C for 30 minutes to form an insulating layer.

(4) Polishing of insulating layer The insulating layer of the inner circuit board on which the insulating layer was formed was polished and cut with a surface grinder under the following conditions. The inner layer circuit board obtained by polishing and cutting the insulating layer was used as an evaluation board A.
Polishing cutting conditions: grinding wheel peripheral speed 500 m / min, table speed 13 m / min, cutting depth 3 μm, total cutting thickness 50 μm, grinding wheel count # 1000

(5) Roughening treatment The inner layer circuit board provided with the polished insulating layer is immersed in a swelling liquid, diethylene glycol monobutyl ether-containing swelling dip / seculigand P, which is a swelling liquid, at 60 ° C. for 5 minutes, and then As a roughening solution, it is immersed in an Acontec Japan Concentrate Compact P (KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 15 minutes, and finally as a neutralizing solution, Atotech Japan It was immersed for 5 minutes at 40 ° C. in a reduction Sholysin securigant P made by the manufacturer.

(6) Plating by semi-additive method In order to form a circuit on the surface of the insulating layer, the inner layer circuit board was immersed in an electroless plating solution containing PdCl ₂ and then immersed in an electroless copper plating solution. After annealing at 150 ° C. for 30 minutes, an etching resist was formed. After pattern formation by etching, copper sulfate electrolytic plating was performed to form a plated conductor layer with a thickness of 30 ± 5 μm. Next, annealing was performed at 180 ° C. for 60 minutes. This circuit board was used as an evaluation board B.

<Surface roughness (Ra1) of the insulating layer surface after polishing and cutting, Maximum cross-sectional height (Rt1) of the roughness curve of the insulating layer surface after polishing and cutting, Surface roughness (Ra2) of the insulating layer surface after roughening treatment ) And measurement of the maximum cross-sectional height (Rt2) of the roughness curve after the roughening treatment>
The surface of the insulating layer of the evaluation substrate A was measured by using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Becoins Instruments Co., Ltd.) with a VSI contact mode and a 50 × lens with a measurement range of 121 μm × 92 μm, and polished. The surface roughness of the subsequent insulating layer surface and the maximum cross-sectional height of the roughness curve were determined. Ra1 and Rt1 were measured by determining the average value of 10 points.

  Ra2 and Rt2 were measured by measuring the surface of the insulating layer after roughening the evaluation substrate A in the same manner as the insulating layer surface of the evaluation substrate A.

<Measurement and evaluation of peel strength with conductor layer>
Cut the 10mm width and 100mm length into the conductor layer of the evaluation board B, peel off one end of the conductor layer, grasp it with a gripping tool, and peel off 35mm vertically at a speed of 50mm / min at room temperature. Load (kgf / cm) was measured. The case where the peel strength was less than 0.40 kgf / cm was evaluated as x, the case where the peel strength was 0.40 kgf / cm or more and less than 0.45 kgf / cm was evaluated as Δ, and the case where the peel strength was 0.45 kgf / cm or more was evaluated as ◯.

<Evaluation of resin residue (laser via reliability) at bottom of via hole>
(1) Underlayer treatment of inner layer circuit board Both sides of a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Panasonic R1515F) on which an inner layer circuit is formed are manufactured by MEC The copper surface was roughened by immersing in CZ8100.

(2) Lamination of resin sheet PET film ("Lumirror R80" manufactured by Toray Industries, Inc.) obtained by releasing the resin varnish produced in Examples and Comparative Examples with an alkyd resin release agent ("AL-5" manufactured by Lintec) The resin composition layer after drying is applied with a die coater so that the thickness of the resin composition layer after drying is 30 μm, and the temperature is 80 ° C. to 120 ° C. The resin sheet was obtained by drying at (average 100 ° C.) for 10 minutes. This resin sheet was laminated using a batch-type vacuum pressure laminator (MVLP-500, manufactured by Meiki Co., Ltd.) so that the resin composition layer was in contact with both surfaces of the inner circuit board. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of resin composition The laminated resin sheet was cured at 180 ° C for 30 minutes to cure the resin composition layer to form an insulating layer.

(4) Formation of via hole Using a CO ₂ laser processing machine (“LC-2E21B / 1C” manufactured by Hitachi Via Mechanics), mask diameter 1.60 mm, focus offset value 0.050, pulse width 25 μs, power 0.66 W The insulating layer was drilled under the conditions of aperture 13, number of shots 2 and burst mode to form a via hole. The top diameter (diameter) of the via hole on the surface of the insulating layer was 50 μm. After the shape of the via hole, the release PET was peeled off.

(5) Roughening treatment The circuit board on which the insulating layer is formed is placed in a swelling liquid (an aqueous solution containing “Swelling Dip Securigant P” manufactured by Atotech Japan, diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes. Roughening solution (Atotech Japan “Concentrate Compact CP”, KMnO ₄ : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 15 minutes and finally neutralization solution (Atotech Japan “Reduction” (Solution Securigant P ", sulfuric acid aqueous solution) at 40 ° C for 5 minutes and then dried at 80 ° C for 30 minutes.

(6) Evaluation of resin residue (laser via reliability) at bottom of via hole The periphery of the bottom of the via hole was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the via hole was measured from the obtained image. The evaluation criteria are shown below.
Evaluation criteria:
○: Maximum smear length is less than 3 μm ×: Maximum smear length is 3 μm or more

<Measurement of elastic modulus and measurement of 1% weight loss temperature>
(1) Preparation of cured product for evaluation A glass cloth base epoxy resin double-sided copper-clad laminate on a release agent-untreated surface of a PET film treated with a release agent (“501010”, thickness 38 μm, 240 mm square, manufactured by Lintec Corporation) A plate (“R5715ES” manufactured by Panasonic Corporation, thickness 0.7 mm, 255 mm square) was overlapped, and the four sides were fixed with a polyimide adhesive tape (width 10 mm) (hereinafter sometimes referred to as “fixed PET film”).

  The resin varnishes produced in Examples and Comparative Examples were applied on the release treatment surface of the above-mentioned “fixed PET film” with a die coater so that the thickness of the resin composition layer after drying was 40 μm. The resin sheet was obtained by drying at 120 ° C. (average 100 ° C.) for 10 minutes.

  Next, the resin composition layer was thermally cured under curing conditions for 90 minutes after being placed in an oven at 180 ° C.

  After thermosetting, the polyimide adhesive tape is peeled off, the cured product is removed from the glass cloth base epoxy resin double-sided copper-clad laminate, and the PET film (“501010” manufactured by Lintec Corporation) is also peeled off to obtain a sheet-like cured product. It was. The obtained cured product is referred to as “evaluated cured product”.

(2) Measurement of elastic modulus The cured product for evaluation was cut into a dumbbell shape No. 1 to obtain a test piece. The test piece was subjected to tensile strength measurement using a tensile tester “RTC-1250A” manufactured by Orientec Co., and the elastic modulus at 23 ° C. was obtained. The measurement was performed according to JIS K7127. This operation was performed three times and the average value is shown in the following table.

(3) Measurement of 1% weight loss temperature (heat resistance evaluation)
The cured product for evaluation was heated from 25 ° C. to 400 ° C. at a heating rate of 10 ° C./min while flowing nitrogen at 250 m 1 / min using a differential thermothermal gravimetric measuring device (TG / DTA6200, manufactured by Seiko Instruments Inc.). Thermogravimetry was performed when the temperature was raised, and a 1% weight loss temperature was determined. The case where the 1% weight loss temperature was 350 ° C. or higher was rated as “◯”, and the case where it was lower than 350 ° C. was marked as “X”.

[Synthesis Example 1]
In a reaction vessel, difunctional hydroxy group-terminated polybutadiene (G-3000, manufactured by Nippon Soda Co., Ltd., number average molecular weight = 3000, hydroxy group equivalent = 1800 g / eq.) 69 g and ipsol 150 (aromatic hydrocarbon-based mixed solvent: Idemitsu) 40 g of petrochemicals) and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. When the temperature became uniform, the temperature was raised to 50 ° C., and 8 g of isophorone diisocyanate (manufactured by Evonik Degussa Japan, IPDI, isocyanate group equivalent = 113 g / eq.) Was added with further stirring, and the reaction was performed for about 3 hours. Next, after cooling the reaction product to room temperature, 23 g of cresol novolak resin (KA-1160, manufactured by DIC, hydroxyl equivalent = 117 g / eq.) And 60 g of ethyl diglycol acetate (manufactured by Daicel) were added. The temperature was raised to 80 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. The confirmation of the disappearance of the NCO peak is regarded as the end point of the reaction, and the reaction product is cooled to room temperature and then filtered through a 100 mesh filter cloth to obtain the component (A) of Synthesis Example 1 having a butadiene structure and a phenolic hydroxyl group (nonvolatile content) 50% by mass) was obtained. The number average molecular weight was 5500.

[Synthesis Example 2]
A flask equipped with a stirrer, a thermometer and a condenser was charged with 292.09 g of ethyl diglycol acetate and 292.09 g of Solvesso 150 (aromatic solvent, manufactured by ExxonMobil) as a solvent, and 100.1 g of diphenylmethane diisocyanate ( 0.4 mol) and 426.6 g (0.2 mol) of polybutadiene diol (hydroxyl value 52.6 KOH-mg / g, molecular weight 2133) were charged and reacted at 70 ° C. for 4 hours. Subsequently, 195.9 g (0.2 mol) of nonylphenol novolac resin (hydroxyl equivalent 229.4 g / eq, average 4.27 functionality, average calculated molecular weight 979.5 g / mol) and ethylene glycol bisanhydro trimellitate 41.0 g ( 0.1 mol), heated to 150 ° C. over 2 hours, and allowed to react for 12 hours, whereby component (A) of Synthesis Example 2 having a butadiene structure and a phenolic hydroxyl group (nonvolatile content 55.2) Mass%).

[Example 1]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 10 parts of 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), naphthalene type epoxy resin 20 parts of "ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent of about 330), 10 parts of glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90-105 g / eq), curing accelerator (Shikoku Chemicals) "1B2PZ", 1 part of 1-benzyl-2-phenylimidazole, 300 parts of component (A) in Synthesis Example 1 (solid content 50%, number average molecular weight: 5500), biphenylaralkyl type maleimide resin (Nippon Kayaku) "MIR-3000-70MT" manufactured, maleimide group equivalent: 275 g / eq, non-volatile content 70% 28.5 parts of a MEK / toluene mixed solution), 14 parts of a carbodiimide resin (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., a carbodiimide equivalent of 216, a toluene solution of 50% by mass of a nonvolatile component), SO-C4 (aminosilane coupling agent ( 950 parts of spherical silica (manufactured by Admatechs Co., Ltd., average particle diameter 1 μm)) and 60 parts of methyl ethyl ketone mixed with Shin-Etsu Chemical Co., Ltd. “KBM573”) and uniformly dispersed with a high-speed rotary mixer, resin A varnish was prepared.

[Example 2]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 10 parts, naphthol type epoxy resin 20 parts of "ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent of about 330), 10 parts of glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90-105 g / eq), curing accelerator (Shikoku Chemicals) "1B2PZ", 1 part of 1-benzyl-2-phenylimidazole, 300 parts of component (A) in Synthesis Example 1 (solid content 50%, number average molecular weight: 5500), biphenylaralkyl type maleimide resin (Nippon Kayaku) "MIR-3000-70MT" manufactured, maleimide group equivalent: 275 g / eq, non-volatile content 70% MEK / toluene mixed solution) 28.5 parts, carbodiimide resin (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216, non-volatile component 50% by mass toluene solution) 14 parts, SO-C2 (aminosilane coupling agent ( 950 parts of spherical silica (manufactured by Admatechs Co., Ltd., average particle size of 0.5 μm)) and 60 parts of methyl ethyl ketone mixed with Shin-Etsu Chemical Co., Ltd. “KBM573”) and uniformly dispersed with a high-speed rotary mixer A resin varnish was prepared.

[Example 3]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 10 parts, naphthol type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. “ESN475V”, epoxy equivalent of about 330) 10 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Co., Ltd. “630LSD”, epoxy equivalent: 90-105 g / eq), curing accelerator (Shikoku Chemicals) "1B2PZ" manufactured by the company, 1 part of 1-benzyl-2-phenylimidazole), 272 parts of component (A) of Synthesis Example 2 (solid content 55.2%), biphenylaralkyl type maleimide resin ("MIR-" manufactured by Nippon Kayaku Co., Ltd.) 3000-70MT ", maleimide group equivalent: 275 g / eq, MEK / toluene mixture with non-volatile content of 70% Solution) 28.5 parts, bisphenol A novolak type epoxy resin ("Mitsubishi Chemical" 157S70 ", epoxy equivalent 210 g / eq) 5 parts, carbodiimide resin (Nisshinbo Chemical" V-03 ", carbodiimide equivalent 216, non-volatile components 16 parts of 50% by weight toluene solution), SO-C2 (spherical silica surface treated with aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) (manufactured by Admatechs, average particle size 0.5 μm)) 1080 parts and 90 parts of methyl ethyl ketone were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.

[Example 4]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 10 parts, naphthol type epoxy resin 20 parts of "ESN475V" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., epoxy equivalent of about 330), 10 parts of glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90-105 g / eq), curing accelerator (Shikoku Chemicals) "1B2PZ", 1 part of 1-benzyl-2-phenylimidazole, 300 parts of component (A) in Synthesis Example 1 (solid content 50%, number average molecular weight: 5500), biphenylaralkyl type maleimide resin (Nippon Kayaku) “MIR-3000-70MT” manufactured by the company, maleimide group equivalent: 275 g / eq, nonvolatile content: 70 MEK / toluene mixed solution) 28.5 parts, carbodiimide resin (Nisshinbo Chemical Co., Ltd. “V-03”, carbodiimide equivalent 216, non-volatile component 50% by weight toluene solution) 4 parts, SO-C2 (aminosilane coupling agent) 950 parts of spherical silica (manufactured by Admatechs, average particle size 0.5 μm) surface-treated with “KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) and 60 parts of methyl ethyl ketone are mixed and dispersed uniformly with a high-speed rotary mixer. A resin varnish was prepared.

[Example 5]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 10 parts, naphthol type epoxy resin (“NSN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 330), 12 parts of glycidylamine type epoxy resin (“630LSD” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90 to 105 g / eq), curing accelerator (Shikoku Chemicals) "1B2PZ", 1 part of 1-benzyl-2-phenylimidazole, 300 parts of component (A) in Synthesis Example 1 (solid content 50%, number average molecular weight: 5500), biphenylaralkyl type maleimide resin (Nippon Kayaku) “MIR-3000-70MT” manufactured by the company, maleimide group equivalent: 275 g / eq, nonvolatile content: 70 MEK / toluene mixed solution) 40 parts, carbodiimide resin (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216, non-volatile component 50% by weight toluene solution) 14 parts, SO-C2 (aminosilane coupling agent (Shin-Etsu) 950 parts of spherical silica (manufactured by Chemical Industry Co., Ltd. “KBM573”) and admixed with 950 parts (average particle size: 0.5 μm) and 60 parts of methyl ethyl ketone were mixed uniformly with a high-speed rotary mixer, A resin varnish was prepared.

[Example 6]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 17 parts of 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio, epoxy equivalent: 169 g / eq), naphthol type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. “ESN475V”, epoxy equivalent of about 330), 10 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Corporation “630LSD”, epoxy equivalent: 90-105 g / eq), 16 parts, curing accelerator (Shikoku Chemicals) “1B2PZ” manufactured by the company, 1 part of 1-benzyl-2-phenylimidazole), 272 parts of the component (A) of the synthesis example 2 (solid content 55.2%), biphenylaralkyl type maleimide resin (“MIR” manufactured by Nippon Kayaku Co., Ltd.) -3000-70MT ", maleimide group equivalent: 275 g / eq, MEK / toluene with a nonvolatile content of 70% 10 parts, carbodiimide resin (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide equivalent 216, toluene solution with 50% by mass of non-volatile components) 16 parts, bisphenol A novolac type epoxy resin (“Mitsubishi Chemical“ 157S70 ”, epoxy) Equivalent 210 g / eq) 5 parts, SO-C2 (spherical silica surface treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) (1080 parts, average particle size 0.5 μm)) 1080 parts And 90 parts of methyl ethyl ketone were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.

[Comparative Example 1]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 10 parts, naphthol type epoxy resin 10 parts of “ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 330, 10 parts of polyalkyleneoxy structure-containing resin (“YX7400” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 440 g / eq), glycidylamine type epoxy resin (Mitsubishi Chemical) "630LSD", 10 parts by epoxy equivalent: 90 to 105 g / eq), 1 part of a curing accelerator ("1B2PZ" by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole), component (A) in Synthesis Example 2 (Solid content 55.2%) 272 parts, active ester type curing agent (“HPC-800 manufactured by DIC Corporation) -65T ", an active group equivalent of about 225, a toluene solution containing 65% by mass of a non-volatile component, and 31 parts of SO-C4 (aminosilane coupling agent (" KBM573 "manufactured by Shin-Etsu Chemical Co., Ltd.)) 960 parts by Mattex, average particle size 1.0 μm)) and 90 parts of methyl ethyl ketone were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.

[Comparative Example 2]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 45 parts of 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), naphthalene type epoxy resin (ESN475V manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 330), 32 parts of naphthol type epoxy resin (“HP4710” manufactured by DIC, epoxy equivalent of 160 to 180 g / eq), glycidylamine type epoxy resin (Mitsubishi Chemical Corporation) “630LSD”, epoxy equivalent: 90 to 105 g / eq) 35 parts, curing accelerator (“1B2PZ” manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, active ester curing agent (manufactured by DIC) "HPC-8000-65T", active group equivalent of about 225, 65 non-volatile components % Toluene solution) 35.4 parts, SO-C4 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) surface-treated spherical silica (manufactured by Admatechs, average particle size 1 μm)) 1340 parts , 28.5 parts of biphenyl aralkyl type maleimide resin (“MIR-3000-70MT” manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution with non-volatile content of 70%), carbodiimide resin (Nisshinbo Chemical Co., Ltd.) 14 parts of "V-03", carbodiimide equivalent 216, 50 mass% nonvolatile component toluene solution) and 250 parts of methyl ethyl ketone were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.

[Comparative Example 3]
Liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 14 parts of 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), naphthol type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. “ESN475V”, epoxy equivalent of about 330) 20 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Corporation “630LSD”, epoxy equivalent: 90-105 g / eq), 13 parts of curing accelerator (Shikoku Chemicals) "1B2PZ", 1 part of 1-benzyl-2-phenylimidazole, 300 parts of component (A) in Synthesis Example 1 (solid content 50%, number average molecular weight: 5500), biphenylaralkyl type maleimide resin (Nippon Kayaku) “MIR-3000-70MT” manufactured by the company, maleimide group equivalent: 275 g / eq, nonvolatile content: 70 28.5 parts of MEK / toluene mixed solution), SO-C2 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)), and spherical silica (manufactured by Admatechs, average particle size of 0.5 μm) )) 950 parts and 120 parts of methyl ethyl ketone were mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish.

[Comparative Example 4]
Liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169 g / eq), 20 parts, naphthol type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd. “ESN475V”, epoxy equivalent of about 330) 20 parts, glycidylamine type epoxy resin (Mitsubishi Chemical Corporation “630LSD”, epoxy equivalent: 90-105 g / eq), curing accelerator (Shikoku Chemicals) "1B2PZ" manufactured by the company, 1 part of 1-benzyl-2-phenylimidazole, 300 parts of the component (A) of Synthesis Example 1 (solid content 50%, number average molecular weight: 5500), carbodiimide resin ("V" manufactured by Nisshinbo Chemical Co., Ltd.) -03 ", carbodiimide equivalent 216, toluene solution of 50% by weight of non-volatile components) 14 parts, SO- 950 parts of spherical silica (manufactured by Admatechs, average particle size 0.5 μm) surface-treated with 2 (aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) and 120 parts of methyl ethyl ketone were mixed. A resin varnish was prepared by uniformly dispersing with a rotary mixer.

The main abbreviations in the table below are as follows.
Synthesis Example 1: Component (A) of Synthesis Example 1 Synthesis Example 2: Component (A) YX7400 of Synthesis Example 2: Polyalkyleneoxy structure-containing resin, ZX1059 manufactured by Mitsubishi Chemical Corporation: Bisphenol A type epoxy resin and bisphenol F type epoxy resin 1: 1 mixture product (mass ratio), epoxy equivalent: 169 g / eq, Nippon Steel & Sumikin Chemical Co., Ltd. 630LSD: glycidylamine type epoxy resin, epoxy equivalent: 90-105 g / eq, Mitsubishi Chemical Corporation ESN475V: naphthol type epoxy Resin, epoxy equivalent of about 330, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. 157S70: bisphenol A novolac type epoxy resin, epoxy equivalent of 210 g / eq, Mitsubishi Chemical Corporation HP-4710: naphthalene type epoxy resin, epoxy equivalent of 160-180 g / eq, DIC Corporation V-03: Carbodiimide resin, Cal Diimide equivalent 216, toluene solution with 50% non-volatile component, MIR-3000-70MT manufactured by Nisshinbo Chemical Co., Ltd .: biphenyl aralkyl type maleimide resin, maleimide group equivalent: 275 g / eq, MEK / toluene mixed solution with 70% non-volatile content, Nippon Kayaku SO-C4 manufactured by Yakuhin Co., Ltd .: Spherical silica surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Admatechs Co., Ltd., average particle size: 1 μm)
SO-C2: Spherical silica surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Admatechs, average particle size 0.5 μm)
1B2PZ: curing accelerator, 1-benzyl-2-phenylimidazole, HPC-8000-65T manufactured by Shikoku Kasei Co., Ltd .: active ester type curing agent, active group equivalent of about 225, toluene solution of 65% by mass of non-volatile components, manufactured by DIC

From the results of Examples 1 to 6, since the insulating layer formed from the resin composition containing the components (A) to (E) has a low elastic modulus of 17 GPa or less, the occurrence of warpage is suppressed. Further, the peel strength is preferably 0.4 kgf / cm or more, and the adhesiveness with the conductor layer is excellent. Further, the 1% weight loss temperature is sufficiently high and excellent in heat resistance, and the resin residue at the bottom of the via hole is suppressed, so that it is understood that the laser via reliability is also excellent. Furthermore, the surface roughness (Ra1) of the insulating layer surface after polishing cutting, the maximum cross-sectional height (Rt1) of the roughness curve of the insulating layer surface after polishing cutting, and the surface roughness (Rt1) of the insulating layer surface after roughening treatment ( It can also be seen that Ra2) and the maximum cross-sectional height (Rt2) of the roughness curve after the roughening treatment are also excellent. On the other hand, in Comparative Examples 1 and 3 to 4 that do not contain the component (C) and / or (D), any one of the peel strength, the 1% weight reduction temperature, and the resin residue at the bottom of the via hole is higher than in Examples 1 to 6. You can see that it is inferior. Moreover, it turns out that the comparative example 2 which does not contain (A) component has a higher elasticity modulus than Examples 1-6, and a peeling strength and the resin residue of a via-hole bottom part are inferior. In Comparative Example 2, Ra2 and Rt2 were not measured.
In addition, even if it does not contain (F) component, although it is different in a grade, it has confirmed that it results in the same result as the said Example.

100 Semiconductor Chip Package 110 Semiconductor Chip 120 Sealing Layer 130 Rewiring Formation Layer (Insulating Layer)
140 Conductor layer (rewiring layer)
150 Solder resist layer 160 Bump

Claims (17)

(A) One or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly (meth) acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule Having a resin,
(B) an epoxy resin having an aromatic structure,
(C) a carbodiimide compound,
A resin composition containing (D) a biphenyl aralkyl type resin (excluding those corresponding to the component (B)), and (E) an inorganic filler.   The resin composition according to claim 1, wherein the cured product obtained by thermosetting the resin composition at 180 ° C for 90 minutes has an elastic modulus at 23 ° C of 17 GPa or less.   The resin composition according to claim 1 or 2, wherein the content of the component (A) is 30% by mass to 85% by mass when the nonvolatile component of the resin composition excluding the component (E) is 100% by mass. object.   (E) The resin composition of any one of Claims 1-3 whose content of a component is 60 mass% or more when the non-volatile component in a resin composition is 100 mass%.   The resin composition according to any one of claims 1 to 4, wherein the component (A) is at least one selected from a resin having a glass transition temperature of 25 ° C or lower and a resin that is liquid at 25 ° C. .   The resin composition according to any one of claims 1 to 5, wherein the component (A) has a functional group capable of reacting with the component (B).   The component (A) has one or more functional groups selected from a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group, and a urethane group. The resin composition as described.   The resin composition according to any one of claims 1 to 7, wherein the component (A) has an imide structure.   (A) The resin composition of any one of Claims 1-8 in which a component has a phenolic hydroxyl group.   (A) The resin composition of any one of Claims 1-9 in which a component has a polybutadiene structure and has a phenolic hydroxyl group.   (D) The resin composition of any one of Claims 1-10 in which a component has a maleimide group in a molecule | numerator.   The resin composition according to claim 1, which is a resin composition for an insulating layer of a semiconductor chip package.   The resin sheet which has a support body and the resin composition layer provided on this support body containing the resin composition of any one of Claims 1-12.   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 of 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.   The semiconductor chip package containing the semiconductor chip sealed with the resin composition of any one of Claims 1-12, or the resin sheet of Claim 13.

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