TW202206553A - Resin compositions - Google Patents

Abstract

Provided is a resin composition in which bending is avoided and which enables acquisition of insulation layers with excellent attachability with conductor layers even in a low light condition. Moreover, provided are a resin sheet using the resin composition, a circuit board, and a semiconductor chip package. To this end, the resin composition comprises: (A) a resin having, in a molecule, at least one structure selected among 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; (B) an epoxy resin having an aromatic structure; (C) a carbodiimide compound; (D) a biphenyl aralkyl-type resin (excluding the component (B)); and (E) an inorganic filler.

Description

resin composition

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

In recent years, the demand for small high-performance electronic devices for smartphones and tablet devices has increased, and along with this, the insulating materials (insulating layers) for semiconductor packaging used in these small electronic devices are also required to be more functional.

For example, an insulating layer used in a wafer-level chip-scale package or a wiring board with an embedded wiring layer is required to suppress warpage that occurs 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 a thermosetting resin composition. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-37083

[The problem to be solved by the invention]

However, the material described in Patent Document 1 is limited in design of the resin composition from the viewpoint of compatibility with other resins, and is limited to use in wafer-level chip-scale packages or wiring boards with embedded wiring layers. Insulation.

The present invention provides a resin composition suitable for forming an insulating layer used in a wafer-level chip scale package or a wiring board provided with an embedded wiring layer, and specifically, provides a resin composition that can suppress the occurrence of warpage and even Resin composition of insulating layer with low roughness and excellent adhesion of conductor layer; and resin sheet, circuit board and semiconductor chip package using the resin composition are provided. [means to solve the problem]

The inventors of the present invention found that by containing: (A) a molecule having a structure selected from the group consisting of polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, and polyalkoxy structure , Resin with more than one structure of polyisoprene structure, polyisobutylene structure and polycarbonate structure, (B) epoxy resin with aromatic structure, (C) carbodiimide compound, (D) combined Phenyl aralkyl-type resins (except those corresponding to component (B)), and (E) inorganic fillers, can suppress the occurrence of warpage and obtain adhesion of the conductor layer even with low roughness. Excellent insulating layer, thus completing the present invention. Furthermore, it was found that the insulating layer was excellent in reliability of laser vias and excellent in heat resistance because the generation of resin residues was suppressed during the formation of laser vias.

That is, the present invention includes the following. [1] A resin composition comprising: (A) In the molecule, it has a structure selected from the group consisting of polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkoxy structure, polyisoprene structure, poly(meth)acrylate structure Resin with one or more structures of isobutylene structure and polycarbonate structure, (B) epoxy resins having an aromatic structure, (C) a carbodiimide compound, (D) biphenyl aralkyl type resins (except those equivalent to component (B)), and (E) Inorganic filler. [2] The resin composition according to [1], wherein the elastic modulus of the cured product at 23° C. after thermally curing the resin composition at 180° C. for 90 minutes is 17 GPa or less. [3] The resin composition according to [1] or [2], wherein the content of the component (A) is 30% by mass when the nonvolatile content of the resin composition excluding the component (E) is 100% by mass ~85% by mass. [4] The resin composition according to any one of [1] to [3], wherein the content of the component (E) is 60 mass % or more when the nonvolatile matter in the resin composition is 100 mass % . [5] The resin composition according to any one of [1] to [4], wherein the component (A) is one or more selected from resins having a glass transition temperature of 25°C or lower and resins that are liquid at 25°C . [6] The resin composition according to any one of [1] to [5], wherein the (A) component has a functional group reactive with the (B) component. [7] The resin composition according to any one of [1] to [6], wherein the component (A) has a group selected from the group consisting of a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group one or more functional groups. [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 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 comprising 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 comprising 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 substrate of [15] and a semiconductor chip mounted on the circuit substrate. [17] A semiconductor chip package comprising a semiconductor chip sealed by the resin composition according to any one of [1] to [12] or the resin sheet according to [13]. [Inventive effect]

According to the present invention, it is possible to provide a resin composition that can obtain an insulating layer with low roughness and excellent adhesion to a conductor layer with suppressed occurrence of warpage; and a resin sheet, circuit board and resin sheet using the resin composition. Semiconductor wafer packaging.

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

[resin composition] The resin composition of the present invention contains (A) a structure selected from the group consisting of polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkoxyl structure, polyalkylene structure Resin with one or more structures of isoprene structure, polyisobutylene structure and polycarbonate structure, (B) epoxy resin having aromatic structure, (C) carbodiimide compound, (D) biphenyl group Aralkyl resins (except those equivalent to (B) component), and (E) inorganic fillers.

By containing (A) component, (B) component, (C) component, (D) component and (E) component in the resin composition, the occurrence of warpage can be suppressed, and even the low roughness and the conductive layer can be obtained. An insulating layer with excellent adhesion. The resin composition may further contain (F) a curing accelerator, (G) a curing agent, and (H) a flame retardant as necessary. Each component contained in the resin composition will be explained in detail below.

<(A) has a structure selected from the group consisting of polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkoxy structure, polyisoprene structure, Resin with one or more structures of polyisobutylene structure and polycarbonate structure> The resin composition of the present invention contains, as the component (A), a molecule having a structure selected from the group consisting of polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkoxyl Resin with one or more structures of structure, polyisoprene structure, polyisobutylene structure and polycarbonate structure. (A) Component has a structure selected from the group consisting of polybutadiene structure, polysiloxane structure, poly(meth)acrylate structure, polyalkylene structure, polyalkoxy structure, polyisoprene structure in the molecule. One or more of the olefin structure, the polyisobutylene structure, and the polycarbonate structure show flexibility. By containing the soft resin such as (A) component, the insulating layer has a low elastic modulus, and the occurrence of warpage can be suppressed. In addition, "(meth)acrylate" means methacrylate and acrylate.

More specifically, the component (A) preferably has a polybutadiene structure selected from the group consisting of polybutadiene structure and hydrogenated polybutadiene, polysiloxane structure such as polysiloxane rubber, poly(methyl) Acrylate structure, polyalkylene structure, polyalkoxy structure, polyisoprene structure, polyisobutylene structure, and polycarbonate structure, one or more kinds of structures, preferably selected from polybutene One or two or more kinds of structures selected from the group consisting of olefin structure, polysiloxane structure, poly(meth)acrylate structure, polyisoprene structure, polyisobutylene structure and polycarbonate structure, more preferably selected from polybutylene One or more structures of diene structure and poly(meth)acrylate structure.

The polyalkylene structure is preferably a polyalkylene structure having 2 to 15 carbon atoms, more preferably a polyalkylene structure having 3 to 10 carbon atoms, and more preferably a polyalkylene structure having 5 to 6 carbon atoms. Alkylene structure. The polyalkoxy structure is preferably a polyalkoxy structure having 2 to 15 carbon atoms, more preferably a polyalkoxy structure having 3 to 10 carbon atoms, and more preferably a polyalkoxy structure having 5 to 5 carbon atoms. 6. Polyalkoxy structure.

The component (A) preferably has a high molecular weight in order to exhibit flexibility, and the number average molecular weight (Mn) is preferably from 1,000 to 1,000,000, more preferably from 5,000 to 900,000. The number average molecular weight (Mn) is the number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

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

The glass transition temperature of the resin having a glass transition temperature (Tg) of 25°C or lower is preferably 20°C or lower, more preferably 15°C or lower. The lower limit of the glass transition temperature is not particularly limited, but can usually be set to -15°C or higher. Moreover, as the resin which is liquid at 25°C, it is preferably a resin which is liquid at 20°C or lower, more preferably a resin which is liquid at 15°C or lower.

As the component (A), from the viewpoint of improving the mechanical strength of the cured product, it is preferable to have a functional group that can react with the component (B) described later. Moreover, as a functional group which can react with (B) component, the functional group which appeared by heating is also included.

In a preferred embodiment, the functional group that can react with the component (B) is one or more functional groups selected from the group consisting of hydroxyl group, carboxyl group, acid anhydride group, phenolic hydroxyl group, epoxy group, isocyanate group and urethane group . Among them, the functional group is preferably a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group, more preferably a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, and an epoxy group, particularly preferably is a phenolic hydroxyl group. When only an epoxy group is contained as a functional group, (A) component does not have an aromatic structure.

One of the preferred embodiments of the component (A) is a butadiene resin. The butadiene resin is preferably a butadiene resin having a liquid state at 25°C or a glass transition temperature of 25°C or lower, more preferably selected from resins containing a hydrogenated polybutadiene skeleton (for example, a resin containing a hydrogenated polybutadiene skeleton). skeleton epoxy resin), butadiene resin containing hydroxyl group, butadiene resin containing phenolic hydroxyl group (resin with polybutadiene structure and phenolic hydroxyl group), butadiene resin containing carboxyl group, acid anhydride containing One or more resins from the group consisting of butadiene resins containing epoxy groups, butadiene resins containing epoxy groups, butadiene resins containing isocyanate groups and butadiene resins containing urethane groups, More preferably, it is a butadiene resin containing a phenolic hydroxyl group. Here, the "butadiene resin" refers to 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. The butadiene structure can be partially or fully hydrogenated. Here, the "resin containing a hydrogenated butadiene skeleton" refers to a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and it 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 from 1,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 7,500 to 30,000, still more preferably from 10,000 to 15,000. Here, the number-average molecular weight (Mn) of the resin is the number-average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

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

Specific examples of the butadiene resin include "Ricon 657" (polybutadiene containing epoxy group), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", and "Ricon 131MA5" manufactured by CRAY VALLEY. , "Ricon 131MA10", "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing acid anhydride group), "JP-100", "JP-200" (epoxidized Polybutadiene), "GQ-1000" (polybutadiene with hydroxyl and carboxyl groups introduced), "G-1000", "G-2000", "G-3000" (polybutadiene with hydroxyl groups at both ends) , "GI-1000", "GI-2000", "GI-3000" (polybutadiene hydrogenated with hydroxyl groups at both ends), "PB3600", "PB4700" (polybutadiene skeleton epoxy resin manufactured by DAICEL) ), "EPOFRIEND A1005", "EPOFRIEND A1010", "EPOFRIEND A1020" (epoxide of styrene, butadiene and styrene block copolymer), "FCA-061L" (hydrogenated poly Butadiene skeleton epoxy resin), "R-45EPT" (polybutadiene skeleton epoxy resin), etc.

Moreover, the resin which has an imide structure can also be used as another preferable embodiment of (A) component. As these (A) components, linear polyimide using hydroxyl-terminated polybutadiene, diisocyanate compound, and tetrabasic acid anhydride as raw materials (JP 2006-37083 A, WO 2008/153208) can be exemplified. Polyimide described in Gazette No. ) etc. The butadiene structure content of the polyimide resin is preferably from 60% by mass to 95% by mass, more preferably from 75% by mass to 85% by mass. For details of the polyimide resin, reference can be made to the descriptions of JP 2006-37083 A and WO 2008/153208 , the contents of which are incorporated into the present specification.

Another preferred embodiment of the component (A) is an acrylic resin. The acrylic resin is preferably an acrylic resin having a glass transition temperature (Tg) of 25°C or lower, more preferably selected from the group consisting of hydroxyl-containing acrylic resins, phenolic hydroxyl-containing acrylic resins, carboxyl-containing acrylic resins, and acid anhydride group-containing acrylic resins Resin, one or more resins from the group consisting of resin, epoxy group-containing acrylic resin, isocyanate group-containing acrylic resin, and urethane group-containing acrylic resin. Here, the "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 from 10,000 to 1,000,000, more preferably from 30,000 to 900,000. Here, the number-average molecular weight (Mn) of the resin is the number-average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

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

Specific examples of acrylic resins include TEISAN RESIN "SG-70L", "SG-708-6", "WS-023", "SG-700AS", "SG-280TEA" (carboxyl group-containing acrylic copolymer resin, acid value 5~34 mgKOH/g, weight average molecular weight 400,000~900,000, Tg-30~5℃), "SG-80H", "SG-80H-3", "SG- P3" (acrylate copolymer resin containing epoxy group, epoxy equivalent weight 4761~14285g/eq, weight average molecular weight 350,000~850,000, Tg11~12℃), "SG-600TEA", "SG-790" ( Hydroxyl-containing acrylate copolymer resin, hydroxyl value 20~40mgKOH/g, weight average molecular weight 500,000~1.2 million, Tg-37~-32℃), "ME-2000", "W-116.3" manufactured by Negami Kogyo Co., Ltd. "(Acrylate copolymer resin containing carboxyl group), "W-197C" (Acrylate copolymer resin containing hydroxyl group), "KG-25", "KG-3000" (Acrylate copolymer resin containing epoxy group )Wait.

Moreover, a preferable embodiment of (A) component is a carbonate resin. The carbonate resin is preferably a carbonate resin having a glass transition temperature of 25°C or lower, more preferably selected from the group consisting of hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins One or more resins in the group consisting of carbonate resin, epoxy group-containing carbonate resin, isocyanate group-containing carbonate resin, and urethane group-containing carbonate resin. Here, the "carbonate resin" refers to a resin containing a carbonate structure, and 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 ranges are also the same.

Specific examples of the carbonate resin include "T6002", "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemical Co., Ltd., "C-1090", "C-2090", and "C-3090" manufactured by KURARAY Corporation (polycarbonate diol).

In addition, linear polyimide (International Publication No. 2016/129541) using hydroxyl-terminated polycarbonate, diisocyanate compound and tetrabasic acid anhydride as raw materials can also be used. The carbonate olefin structure content of the polyimide resin is preferably from 60% by mass to 95% by mass, more preferably from 75% by mass to 85% by mass. Details of the polyimide resin can be found in International Publication No. 2016/129541, the contents of which are incorporated into this specification.

Furthermore, preferable one embodiment of the component (A) is a polysiloxane resin, an alkylene resin, an alkylene resin, an isoprene resin, and an isobutylene resin.

Specific examples of polysiloxane resins include "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shin-Etsu Polysiloxane Co., Ltd., amino-terminated polysiloxanes, and tetrabasic acid anhydrides as raw materials The linear polyimide (International Publication No. 2010/053185) and the like. Specific examples of the alkylene resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fiber Corporation, and "YX-7180" manufactured by Mitsubishi Chemical Corporation (resin containing an alkylene structure having an ether bond) Wait. Specific examples of alkylene oxide resins include "EXA-4850-150", "EXA-4816", "EXA-4822" manufactured by DIC Corporation, "EP-4000", "EP-4003" manufactured by ADEKA Corporation, "EP-4010" and "EP-4011", "BEO-60E" and "BEO-20E" manufactured by Nippon Chemical Corporation, and "YL7175" and "YL7410" manufactured by Mitsubishi Chemical Corporation. Specific examples of the isoprene resin include "KL-610" and "KL613" manufactured by KURARAY Corporation. 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.

Furthermore, as a preferable embodiment of the component (A), acrylic rubber particles, polyamide fine particles, polysiloxane particles, etc. are exemplified. Specific examples of acrylic rubber particles include chemical cross-linking treatment of resins showing rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, acrylic rubber, etc., and resins that are insoluble or infusible in organic solvents. Specific examples of microparticles are XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), STAFYROID AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (the above are manufactured by GANTZ Chemical Co., Ltd.), PARALOID EXL2655, EXL2602 (the above are Kureha Chemical Industry Co., Ltd. system) etc. Specific examples of the polyamide microparticles can be aliphatic polyamides such as nylon, and any of those having a soft backbone such as polyamide imide can be used, for example, VESTO SINT 2070 (DAICEL HUELS Corporation) or SP500 (Toray Corporation), etc.

The content of the (A) component in the resin composition is preferably 85 mass % or less, more preferably 85 mass % or less, when the non-volatile content of the resin composition excluding the (E) component is 100 mass % from the viewpoint of imparting flexibility It is 80 mass % or less, More preferably, it is 75 mass % or less, More preferably, it is 73 mass % or less. Moreover, the lower limit is preferably at least 30 mass %, more preferably at least 35 mass %, still more preferably at least 45 mass %, still more preferably at least 55 mass %.

<(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 so-called aromatic structure is generally defined as an aromatic chemical structure, including polycyclic aromatics and aromatic heterocycles.

Examples of epoxy resins having an aromatic structure include xylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AF type epoxy resins. Oxygen resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tertiary butyl-catechol type epoxy resin, Naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin with aromatic structure, glycidyl ester type epoxy resin with aromatic structure, cresol novolac type Epoxy resin, biphenyl type epoxy resin, chain aliphatic epoxy resin with aromatic structure, epoxy resin with butadiene structure with aromatic structure, alicyclic epoxy resin with aromatic structure , Heterocyclic epoxy resin, epoxy resin containing spiro ring with aromatic structure, cyclohexane dimethanol type epoxy resin with aromatic structure, naphthyl ether type epoxy resin, trihydroxy epoxy resin with aromatic structure Methyl type epoxy resin, tetraphenylethane type epoxy resin, aminophenol type epoxy resin, etc. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types. The component (B) is preferably at least one selected from the group consisting of 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 is preferably an epoxy resin having two or more epoxy groups in one molecule. It is preferable that at least 50 mass % or more is the epoxy resin which has 2 or more epoxy groups in 1 molecule when the nonvolatile content of the epoxy resin which has an aromatic structure is made into 100 mass %. Among them, epoxy resins having two or more epoxy groups in one molecule and being liquid at a temperature of 20° C. (hereinafter referred to as “liquid epoxy resins”) and epoxy resins having three or more epoxy groups in one molecule are preferably included. Epoxy resin (hereinafter referred to as "solid epoxy resin") which is based on a solid state at a temperature of 20°C. By using together a liquid epoxy resin and a solid epoxy resin as the epoxy resin having an aromatic structure, a resin composition having excellent flexibility can be obtained. In addition, the rupture strength of the cured product of the resin composition is also improved.

The liquid epoxy resin is preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, and a glycidyl ester type ring having an aromatic structure Oxygen resin, glycidylamine type epoxy resin with aromatic structure, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton with aromatic structure, cyclohexanedimethanol with aromatic structure Type epoxy resin, aminophenol type epoxy resin and epoxy resin with butadiene structure with aromatic structure, more preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin type epoxy resin, aminophenol type epoxy resin and naphthalene type epoxy resin, more preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, aminophenol type epoxy resin. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, "828US" and "jER828EL" (bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation) epoxy resin), "jER806", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin) ), "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "EX-721" (glycidyl ester type epoxy resin manufactured by NAGASE CHEM TEX Corporation) Epoxy resin), "CELLOXIDE 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by DAICEL, "ZX1658", "ZX1658GS" (liquid 1,4-glycidol) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. cyclohexane). These may be used individually by 1 type, or may be used in combination of 2 or more types.

The solid epoxy resin is preferably a naphthalene-type tetrafunctional epoxy resin, a cresol novolak-type epoxy resin, a dicyclopentadiene-type epoxy resin having an aromatic structure, a trisphenol-type epoxy resin, and a naphthol. type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin , preferably naphthalene-type 4-functional epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthyl ether-type epoxy resin, and more preferably naphthalene-type 4-functional epoxy resin, naphthyl ether-type epoxy resin resin. Specific examples of solid epoxy resins include "HP-4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), "N-type tetrafunctional epoxy resin" manufactured by DIC Corporation. -690" (cresol novolak epoxy resin), "N-695" (cresol novolak epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200" -7200H", "HP-7200HHH" (dicyclopentadiene epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthyl ether type epoxy resin), "EPPN-502H" (trisphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., manufactured by Mitsubishi Chemical Corporation "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX7760" (bisphenol AF type epoxy resin), "YX8800" (anthracene type epoxy resin) Epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" (Fine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" manufactured by Mitsubishi Chemical Corporation (solid form Bisphenol A epoxy resin), "jER1031S" (tetraphenylethane epoxy resin), "157S70" (bisphenol novolac epoxy resin), "YX4000HK" (xylenol) manufactured by Mitsubishi Chemical Corporation type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" manufactured by Mitsubishi Chemical Corporation (Fine type epoxy resin) , "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These may be used individually by 1 type, or may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (B), the ratio by mass (solid epoxy resin: liquid epoxy resin) is preferably 1:0.1 to 1 in terms of mass ratio : Range of 15. By making the amount ratio of the liquid epoxy resin to the solid epoxy resin within this range, the following effects are obtained: i) when used in the form of a resin sheet, the adhesiveness is kept moderate; ii) when used in the form of a resin sheet At the same time, sufficient flexibility is obtained, workability is improved, and iii) a hardened product with sufficient rupture strength can be obtained, and the like. From the viewpoint of the effects of the above i) to iii), the ratio by mass of the liquid epoxy resin to the solid epoxy resin (solid epoxy resin: liquid epoxy resin) is more preferably 1. : a range of 0.3 to 1:10, and more preferably a range of 1:0.6 to 1:8.

The content of the epoxy resin having an aromatic structure in the resin composition is preferably 100% by mass of the nonvolatile content in the resin composition from the viewpoint of obtaining an insulating layer exhibiting mechanical strength and insulation reliability. 1 mass % or more, more preferably 2 mass % or more, still more preferably 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 effects of the present invention are exhibited, but is preferably 10 mass % or less, more preferably 8 mass % or less, and still more preferably 5 mass % or less.

In addition, the content of the epoxy resin having an aromatic structure in the resin composition is based on the viewpoint of obtaining an insulating layer exhibiting mechanical strength and insulation reliability, and the nonvolatile content of the resin composition excluding the (E) component is set to 100. In the case of mass %, it is preferably at least 1 mass %, more preferably at least 2 mass %, and still more preferably at least 3 mass %. 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 it is preferably 30 mass % or less, more preferably 25 mass % or less, still more preferably 20 mass % or less.

The epoxy equivalent of the epoxy resin having an aromatic structure is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, still more preferably 110 to 1000. By making it into this range, the crosslinking density of hardened|cured material is sufficient and the insulating layer with low surface roughness is kept. In addition, the epoxy equivalent can be measured based on JIS K7236, and it is the resin mass containing 1 equivalent of epoxy groups.

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

<(C) Carbodiimide compound> The resin composition of this invention contains a carbodiimide compound as (C)component. The carbodiimide compound is a compound having one or more carbodiimide groups (-N=C=N-) in one molecule, and by containing the component (C), excellent adhesion to the conductor layer can be maintained In particular, by using the insulating layer 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 maintained. The carbodiimide compound is preferably a compound having two or more carbodiimide groups in one molecule. A carbodiimide compound may be used individually by 1 type, or may be used in combination of 2 or more types.

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

(式中，X表示伸烷基、伸環烷基或伸芳基，該等亦可具有取代基，p表示1~5之整數，X存在複數時，該等可相同亦可不同，*表示鍵結鍵)。

(In the formula, X represents an alkylene group, a cycloalkylene group or an aryl group, which may also have substituents, p represents an integer of 1 to 5, and when X exists in plural, these may be the same or different, and * represents bond key).

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 does not include the number of carbon atoms of the substituent. Preferable examples of the alkylene group include methylene group, ethylidene group, propylidene group, and butylene group.

The number of carbon atoms of the cycloextended alkyl group represented by X is preferably from 3 to 20, more preferably from 3 to 12, still more preferably from 3 to 6. The number of carbon atoms does not include the number of carbon atoms of the substituent. As a preferable example of this cycloextended alkyl group, a cycloextended propyl group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group are exemplified.

The aryl extended 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 in the aryl extended group is preferably 6-24, more preferably 6-18, still more preferably 6-14, still more preferably 6-10. The number of carbon atoms does not include the number of carbon atoms of the substituent. Preferred examples of the arylidene group include a phenylene group, a naphthylene group, and an anthracene group.

When combined with the component (D), X is preferably an alkylene group or a cycloalkylene group from the viewpoint of realizing an insulating layer with better heat resistance, laser via reliability, and adhesion to the conductor layer. It may have a substituent.

The alkylidene, cycloalkylene or arylidene 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 cycloalkoxy group, an aryl group, an aryloxy group, an aryl group, and an aryloxy group. The halogen atom used as a substituent is, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group and the alkoxy group used as the substituent may be either linear or branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 6, 1~4, 1~3. The number of carbon atoms of the cycloalkyl group and the cycloalkoxy group used as a substituent is preferably from 3 to 20, more preferably from 3 to 12, still more preferably from 3 to 6. The aryl group used as a substituent is a group obtained by removing a hydrogen atom on one aromatic ring from an aromatic hydrocarbon, and the number of carbon atoms is preferably 6-24, more preferably 6-18, still more preferably 6-14, Better yet, 6 to 10. The number of carbon atoms of the aryloxy group used as a substituent is preferably from 6 to 24, more preferably from 6 to 18, still more preferably from 6 to 14, still more preferably from 6 to 10. The acyl group used as a substituent refers to a group represented by the formula: -C(=O)-R ¹ (in the formula, R ¹ represents an alkyl group or an aryl group). The alkyl group represented by R ¹ may be either straight-chain or branched, and the number of carbon atoms is preferably 1-20, more preferably 1-10, still more preferably 1-6, 1-4, 1~3. The number of carbon atoms of the aryl group represented by R ¹ is preferably 6-24, more preferably 6-18, still more preferably 6-14, still more preferably 6-10. The aryloxy group used as a substituent means a group represented by the formula: -OC(=O)-R ¹ (in the formula, R ¹ represents the same meaning as described above). Among them, the substituent is preferably an alkyl group, an alkoxy group and an acyloxy group, and more preferably an alkyl group.

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

In formula (1), when X has plural numbers, these may be the same or different. In a preferred embodiment, at least one X is an alkylene group or a cycloalkylene group, which may have substituents.

In a preferred embodiment, the carbodiimide compound is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass when the mass of the entire molecule of the carbodiimide compound is 100% by mass. % by mass or more, more preferably 80% by mass or more or 90% by mass or more, contains the structure represented by the formula (1). In addition to the terminal structure, the carbodiimide compound may be substantially constituted by the structure represented by the formula (1). The terminal structure of the carbodiimide compound is not particularly limited, but examples thereof include an alkyl group, a cycloalkyl group, and an aryl group, and 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 which the group represented by X may have. In addition, the substituent which the group used for the terminal structure may have is the same as the substituent which the group represented by X may have.

The weight average molecular weight of the carbodiimide compound is preferably at least 500, more preferably at least 600, still more preferably at least 700, still more preferably at least 800, from the viewpoint of suppressing the generation of outgassing during curing of the resin composition. , especially preferably above 900 or above 1000. Also, from the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the carbodiimide compound is preferably 5,000 or less, more preferably 4,500 or less, still more preferably 4,000 or less, still more preferably 3,500 or less, particularly preferably Below 3000. The weight average molecular weight of the carbodiimide compound can be measured by, for example, a gel permeation chromatography (GPC) method (in terms of polystyrene).

Moreover, a carbodiimide compound may contain an isocyanate group (-N=C=O) in a molecule|numerator derived from the manufacturing method. The isocyanate group content (also referred to as "NCO content") in the carbodiimide compound is preferably 5 from the viewpoint of obtaining a resin composition exhibiting good storage stability, and from the viewpoint of realizing an insulating layer exhibiting desired characteristics The mass % or less is more preferably 4 mass % or less, still more preferably 3 mass % or less, still more preferably 2 mass % or less, and particularly preferably 1 mass % or less or 0.5 mass % or less.

A commercial item can be used as a carbodiimide compound. Examples of commercially available carbodiimide compounds include CARBODILITE (registered trademark) V-02B, V-03, V-04K, V-07 and V-09 manufactured by Nisshinbo Chemical Co., Ltd., and STABAXOL manufactured by RHEIN CHEMIE Co., Ltd. (registered trademark) P, P400 and HYCASYL510.

The content of the component (C) is included in the resin composition excluding the component (E) from the viewpoint of obtaining an insulating layer excellent in any of the characteristics of heat resistance, laser via reliability, and adhesion to the conductor layer. When the nonvolatile content is 100% by mass, it is preferably at least 0.1% by mass, more preferably at least 0.3% by mass, and still more preferably at least 0.5% by mass. The upper limit of the content of the carbodiimide compound is not particularly limited, but is preferably at most 10% by mass, more preferably at most 8% by mass, and still more preferably at most 5% by mass.

<(D) Biphenyl aralkyl type resin (except those equivalent to (B) component)> The resin composition of the present invention contains a biphenyl aralkyl type resin as the component (D) (except those corresponding to the component (B)). By containing the component (D), the insulating layer with excellent adhesion to the conductor layer can be maintained, and especially, by using in combination with the component (C), heat resistance, laser via reliability, and contact with the conductor can be maintained. An insulating layer with excellent adhesion of layers. In addition, in general, biphenyl aralkyl resins tend to have low miscibility and low compatibility with soft resins, but exhibit particularly good compatibility with the above-mentioned (A) component.

(式中，R¹ 分別獨立表示氫原子、碳原子數1~5之烷基、或苯基，R² 分別獨立表示馬來醯亞胺基、氰酸酯基或胺基，n為平均值且表示1＜n≦5，m分別獨立表示1~5之整數)。Although the component (D) is not particularly limited as long as it has a biphenyl aralkyl structure having no epoxy group, it is preferably a resin represented by the following formula (2).

(In the formula, R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, R ² independently represents a maleimide group, a cyanate ester group or an amine group, and n is an average value And it means 1<n≦5, and m independently represents an integer from 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 still more preferably a methyl group. The alkyl group having 1 to 5 carbon atoms may be linear, branched, or cyclic, and is preferably a linear alkyl group. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tertiary butyl group, a 2-butyl group, an n-pentyl group, and the like.

Among these, R ¹ preferably represents a hydrogen atom, a methyl group or a phenyl group from the viewpoint of maintaining an insulating layer excellent in adhesion to the conductor layer.

R ² independently represents a maleimide group, a cyanate group, or an amine group, and is more preferably a maleimide group from the viewpoint of maintaining an insulating layer excellent in adhesion to the conductor layer.

m independently represents an integer from 1 to 5. m preferably represents an integer from 1 to 4, more preferably represents an integer from 1 to 3, and more preferably represents 1.

n is an average value and represents 1<n≦5. Solvent solubility becomes favorable as n is 5 or less. n can be calculated from the value of the weight average molecular weight of the resin represented by the formula (2).

(式中，R¹ 及n可與式(2)中者相同)。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 the formula (2)).

(D) A commercial item can be used for component. As a commercially available component (D), for example, MIR-3000 and MIR-3000-70T manufactured by Nippon Kayaku Co., Ltd. are exemplified.

The content of the component (D) is included in the resin composition excluding the component (E) from the viewpoint of obtaining an insulating layer excellent in any of the characteristics of heat resistance, laser via reliability, and adhesion to the conductor layer. When the nonvolatile content is 100% by mass, it is preferably at least 0.3% by mass, more preferably at least 0.5% by mass, and still more preferably at least 1% by mass. The upper limit of the content of the component (D) is not particularly limited, but is preferably at most 25% by mass, more preferably at most 20% by mass, and more preferably at most 15% by mass.

<(E) Inorganic fillers> The resin composition contains (E) an inorganic filler. The material of the inorganic filler is not particularly limited, such as silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite , Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, 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, etc. Among these, silica is particularly preferred. And the silica is preferably spherical silica. The inorganic filler may be used alone or in combination of two or more.

The average particle size of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, still more preferably 2.2 μm or less, and still more Preferably it is 2 micrometers or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1 μm or more. Examples of commercially available inorganic fillers having such an average particle size include "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatechs, and "UFP-30" manufactured by Denki Chemical Industries, Ltd. , TOKUYAMA "SILFIL NSS-3N", "SILFIL NSS-4N", "SILFIL NSS-5N", Admatechs "SC2500SQ", "SO-C6", "SO-C4", "SO-C2", "SO-C1" etc.

The average particle size of the inorganic filler can be based on the Mie scattering theory, and the laser diffraction can be used. measured by scattering method. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis using a laser diffraction particle size distribution analyzer, and the median diameter can be measured as the average particle size. As a measurement sample, what disperse|distributed an inorganic filler in water with an ultrasonic wave can be used suitably. As the laser diffraction particle size distribution analyzer, "LA-500" manufactured by Horiba, Ltd., etc. can be used.

Inorganic fillers, from the viewpoint of improving moisture resistance and dispersibility, are preferably aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, and organosilicon Treatment with one or more surface treatment agents such as azane compounds and titanate-based coupling agents. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidyloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. , "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-term) manufactured by Shin-Etsu Chemical Co., Ltd. chain epoxy silane coupling agent), etc.

The content of the inorganic filler in the resin composition is preferably 60 mass % or more, more preferably 70 mass % when the non-volatile content in the resin composition is 100 mass % from the viewpoint of obtaining an insulating layer with a low thermal expansion coefficient. % or more, and more preferably 75% by mass or more. From the viewpoint of the mechanical strength of the insulating layer, particularly the elongation, 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.

<(F) Hardening accelerator> The resin composition may contain (F) a hardening accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanamine-based curing accelerators, metal-based curing accelerators, and the like, preferably phosphorus-based curing accelerators and amine-based curing accelerators A hardening accelerator, an imidazole-based hardening accelerator, and a metal-based hardening accelerator are more preferably an amine-based hardening accelerator, an imidazole-based hardening accelerator, or a metal-based hardening accelerator. A hardening accelerator may be used individually by 1 type, or may be used in combination of 2 or more types.

Examples of phosphorus-based hardening accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenyl borate, tetrabutylphosphonium decanoate, (4-methylphosphonium decanoate) Phenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutylphosphonium decanoate .

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-sam(dimethylaminomethyl) Phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-diazabicyclo(5,4,0 )-undecene.

Examples of imidazole-based hardening accelerators include, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole. , 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate acid salt, 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-dihydroxymethylimidazole Hydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazole The imidazole compound such as linoline and the adduct of the imidazole compound and the epoxy resin are preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

A commercial item can also be used as an imidazole type hardening accelerator, for example, "P200-H50" by Mitsubishi Chemical Corporation etc. are mentioned.

Examples of the guanamine-based curing accelerator include dicyandiamide, 1-methylguanamine, 1-ethylguanamine, 1-cyclohexylguanamine, 1-phenylguanamine, 1-(o-toluene) base) guanamine, dimethylguanamine, diphenylguanamine, trimethylguanamine, tetramethylguanamine, pentamethylguanamine, 1,5,7-triazabicyclo [4.4.0] Dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanamine, 1-ethylbiguanamine, 1-n-butyl Biguanamine - Phenyl biguanamine, 1-(o-tolyl) biguanamine, etc., preferably dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

The metal-based hardening accelerator is not particularly limited, and examples thereof include organometallic complexes and organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II) acetylacetonate, cobalt(III) acetylacetonate, and organocopper such as copper(II) acetylacetonate. Complexes, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate compounds, organic manganese complexes such as manganese (II) acetylacetonate, etc. Examples of organometallic salts are, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

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

<(G) Hardener> The resin composition may contain (G) a hardener. The hardener is not particularly limited as long as it has a function of hardening the resin such as the component (B), and examples thereof include phenol-based hardeners, naphthol-based hardeners, active ester-based hardeners, benzoxazine-based hardeners, and Cyanate-based hardener, etc. A hardener may be used individually by 1 type, and may be used in combination of 2 or more types. (G) Component is preferably at least one selected from a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, and a cyanate-based hardener, more preferably a phenol-based hardener and an active ester-based hardener One or more hardeners.

From the viewpoint of heat resistance and water resistance, the phenol-based hardener and the naphthol-based hardener are preferably a phenol-based hardener having a novolak structure or a naphthol-based hardener having a novolak structure. In addition, from the viewpoint of the adhesiveness with the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a phenol-based curing agent containing a triazine skeleton is more preferable. Among them, a phenol novolac hardener containing a triazine skeleton is preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.

Specific examples of phenol-based hardeners and naphthol-based hardeners include, for example, "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemical Co., Ltd., "NHN" manufactured by Nippon Kayaku Co., Ltd. CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" manufactured by Nippon Steel & Sumitomo Metal Corporation, "SN375", "SN395" manufactured by DIC Corporation "TD-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 Kwanrong Chemical Co., Ltd.

The active ester-based curing agent is not particularly limited, but in general, it is preferable to use, for example, phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., which have two or more reactions in one molecule. Compounds with high activity. The active ester-based hardener is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. The carboxylic acid compound is exemplified by, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. The phenolic compound or naphthol compound is exemplified by hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 ,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, phloroglucin, dicyclopentadiene diphenol compound, Phenolic novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing 2 molecules of phenol in 1 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 acetyl compound of a phenol novolak, and a benzyl compound containing a phenol novolak are preferred. The active ester compound is preferably an active ester compound containing a naphthalene structure or an active ester compound containing a dicyclopentadiene-type diphenol structure. In addition, the "dicyclopentadiene-type diphenol structure" refers to a bivalent structure composed of phenylene-dicyclopentadiene-phenylene.

Examples of commercially available active ester-based hardeners include active ester compounds containing dicyclopentadiene-type diphenol structures, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC- 8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC Corporation), "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and an example of an active ester compound of acetylated phenol novolak It is "DC808" (manufactured by Mitsubishi Chemical Corporation), the active ester compound of phenol novolak's benzyl compound is listed as "YLH1026" (manufactured by Mitsubishi Chemical Corporation), and the active ester hardener of phenol novolak's acetyl compound is listed as " "DC808" (manufactured by Mitsubishi Chemical Corporation), active ester hardeners of phenol novolac benzyl compounds are listed as "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) company), etc.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

Examples of the cyanate-based hardener include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'- Methylene bis(2,6-dimethylphenylcyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanato)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanato-3,5-dimethylphenyl)methane, 1,3-Bis(4-cyanatophenyl-1-(methylethylene))benzene, bis(4-cyanatophenyl)sulfide and bis(4-cyanatophenyl) Bi-functional cyanate resins such as base) ethers, polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs, etc., and prepolymers formed by partial triazineization of these cyanate resins. Commercially available cyanate-based hardeners include "PT30" and "PT60" (both are novolac type polyfunctional cyanate resins), "BA230", "BA230S75" (bisphenol A A part or all of the dicyanate is triazineized into a prepolymer of a trimer), etc.

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

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

As the flame retardant, commercially available products such as "HCA-HQ" manufactured by Sanko Co., Ltd., "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd., and the like can be used.

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but when the nonvolatile content in the resin composition is 100% by mass, it is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass % by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass.

<(I) Optional additives> The resin composition may further contain other additives as needed, and the other additives include, for example, organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds, as well as binders, tackifiers, antifoaming agents, leveling agents, densers, etc. Resin additives such as adhesion imparting agents and colorants.

<Physical properties of resin composition> The resin composition of the present invention has an elastic modulus at 23°C of preferably 17GPa or less, more preferably 16GPa or less, 15GPa or less, 14GPa or less, or 13GPa or less, in order to suppress warpage of the cured product after thermal curing at 180°C for 90 minutes. The lower limit is not particularly limited, but may be, for example, 5GPa or more, 6GPa or more, and 7GPa or more. When the elastic modulus is 17 GPa or less, an insulating layer in which warpage of the cured product is suppressed can be obtained. The above-mentioned elastic modulus can be measured according to the method described in <Measurement of elastic modulus and measurement of 1% weight loss temperature> described later.

After the resin composition of the present invention is thermally cured at 180° C. for 30 minutes, the cured product exhibits excellent adhesion with the conductor layer, that is, excellent peel strength (peel strength) with the conductor layer. The peel strength is preferably at least 0.4 kgf/cm, more preferably at least 0.45 kgf/cm, still more preferably at least 0.5 kgf/cm. 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. The evaluation of the adhesiveness with the conductor layer can be performed according to the method described in <Measurement and Evaluation of the Peeling Strength with the Conductor Layer> which will be described later.

The cured product of the resin composition of the present invention after thermal curing at 180° C. for 90 minutes exhibits the characteristic of having a 1% weight loss temperature of 350° C. or higher, and thus exhibits the characteristic of being excellent in heat resistance. The 1% weight reduction temperature is preferably at least 350°C, more preferably at least 355°C, still more preferably at least 360°C. The upper limit value of the 1% weight reduction temperature is not particularly limited, but can be set to 500°C or lower. The evaluation of the 1% weight loss temperature can be measured according to the method described in the below-mentioned <Measurement of Elastic Modulus and Measurement of 1% Weight Loss Temperature>.

When the resin composition of the present invention is thermally hardened at 180° C. for 30 minutes and the cured product forms through holes, the cured product residue length (smear length) at the bottom of the through hole is short. The smear length is preferably not more than 3 μm, more preferably 2.5 μm or less, and still more preferably 2 μm or less. The lower limit is not particularly limited, and may be 0.1 μm or more.

The resin composition of the present invention can maintain an insulating layer with suppressed warpage, excellent heat resistance, and excellent adhesion to the conductor layer, and has good compatibility with the component (A) because it contains the components (B) to (D). . Therefore, the resin composition of the present invention can be preferably used as a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for an insulating layer of a semiconductor chip package), for forming a circuit board (including a printed wiring board) The resin composition of the insulating layer (resin composition for the insulating layer of the circuit board) can also be used as a resin composition for forming the interlayer insulating layer between the conductor layers by plating (the conductor layer is formed by plating). The resin composition for the interlayer insulating layer of the circuit board). Further, the resin composition of the present invention can also be preferably used as a resin composition for sealing a semiconductor wafer (resin composition for sealing a semiconductor wafer), a resin composition for forming wiring on a semiconductor wafer (semiconductor wafer wiring forming with resin composition).

[resin sheet] The resin sheet of the present invention includes a support body and a resin composition layer bonded to the support body, and the resin composition layer is formed of 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, still more 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. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be set to 1 μm or more, 5 μm or more, 10 μm or more, or the like.

As the support, for example, a film made of a plastic material, a metal foil, a mold release paper, etc. are exemplified, and a film or a metal foil made of a plastic material is preferable.

When a film made of a plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as ""PET"). Polyester such as PEN”), polycarbonate (hereinafter sometimes referred to as “PC”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether Sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

The support body may be subjected to matte treatment and corona treatment on the surface to be joined to the resin composition layer.

In addition, as a support, it can also be used as a support with a mold release layer having a mold release layer on the surface to be joined to the resin composition layer. The mold release agent used in the mold release layer as the support with the mold release layer is, for example, one selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. The above release agent. Commercially available products can also be used as the support with a release layer, such as "SK-1", "AL- 5", "AL-7", "LUMIRROR T60" manufactured by Toray Corporation, "PUREX" manufactured by Teijin Corporation, "UNIPEEL" manufactured by YUNICHIKA Corporation, etc.

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

The resin sheet can be produced by, for example, dissolving a resin composition in an organic solvent to prepare a resin varnish, applying the resin varnish on a support using a die coater or the like, and drying to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone, ethyl acetate, butyl acetate, cellolytic acetate, propylene glycol monomethyl ether acetate, and carbamide. Acetates such as bisphenol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetate Amide-based solvents such as amine (DMAc) and N-methylpyrrolidone, etc. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

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

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

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

The sheet-like fiber substrate used for the prepreg is not particularly limited, and commonly used substrates for the prepreg, such as glass cloth, aramid nonwoven, and liquid crystal polymer nonwoven, 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 still more preferably 600 μm or less. The lower limit of the thickness of the sheet-like fiber base material is not particularly limited, but is usually 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

The prepreg can be produced by a conventional method such as a hot melt method and a solvent method.

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

The resin sheet of the present invention can be preferably used in the manufacture of semiconductor chip packages to form insulating layers (insulation resin sheets for semiconductor chip packages). For example, the resin sheet of the present invention can be preferably used to form an insulating layer of a circuit board (resin sheet for an insulating layer of a circuit board), and can be further preferably used to form an interlayer insulating layer of a conductor layer by plating (by means of plating). For interlayer insulating layers of circuit boards where conductor layers are formed by plating). As examples of packages using these substrates, FC-CSP, MIS-BGA packages, and ETS-BGA packages are exemplified.

Furthermore, the resin sheet of the present invention can be preferably used for sealing a semiconductor wafer (resin sheet for sealing a semiconductor wafer) or for forming wiring on a semiconductor wafer (resin sheet for forming a semiconductor wafer wiring), and can be preferably used for, for example, fan-out. Type WLP (Wafer Level Package), fan-in WLP, fan-out PLP (Panel Level Package), fan-in PLP, etc. Moreover, MUF (Molding Under Filling) material etc. which are used after connecting a semiconductor chip to a board|substrate can also be used suitably. Resin Sheet of the Present Invention The resin sheet of the present invention can be suitably used for other wide applications requiring high insulation reliability, for example, for forming an insulating layer of a circuit board such as a printed wiring board.

[circuit board] The circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention. The manufacturing method of the circuit board of the present invention comprises the following steps: (1) The step of preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one side of the substrate, (2) The step of laminating the resin sheet of the present invention on the base material with the wiring layer and thermosetting to form the insulating layer by embedding the wiring layer in the resin composition layer, (3) The step of connecting wiring layers between layers. Moreover, the manufacturing method of a circuit board may include the step of (4) removing a board|substrate.

The step (3) is not particularly limited as long as the wiring layers can be connected between layers, but is preferably at least one of the step of forming a through hole in the insulating layer, the step of forming the wiring layer, and the step of grinding or grinding the insulating layer to expose the wiring layer .

<Step (1)> Step (1) is a step of preparing a wiring layer-attached substrate having a substrate and a wiring layer provided on at least one side of the substrate. Generally, the substrate with a wiring layer has a first metal layer and a second metal layer of a part of the substrate on both sides of the substrate, and has a wiring layer on the surface opposite to the surface on the substrate side of the second metal layer. Specifically, a dry film (photosensitive resist film) is laminated on a base material, and is exposed and developed under specific conditions using a photomask to form a patterned dry film. After forming a wiring layer by an electrolytic plating method using the developed dry film as a plating mask, the patterned dry film is peeled off. In addition, it is not necessary to have the first metal layer and the second metal layer.

Examples of substrates include substrates such as glass epoxy substrates, metal substrates (stainless steel or cold rolled steel sheet (SPCC), etc.), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. A metal layer such as copper foil can also be formed on the surface of the substrate. Moreover, metal layers, such as a 1st metal layer, a 2nd metal layer (for example, the ultra-thin copper foil with a carrier made by Mitsui Metals Co., Ltd., trade name "Micro Thin") may be formed on the surface.

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

The lamination conditions of the base material and the dry film are the same as the conditions for laminating the resin sheet in a manner of embedding the wiring layer in the step (2) described later, and the preferred range is also the same.

After the dry film is laminated on the substrate, the dry film is exposed and developed under specific conditions using a photomask for forming a desired pattern.

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 still more preferably 5/ 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 on the entire wiring layer. The minimum pitch of the wiring layers may be 40 μm or less, 36 μm or less, or 30 μm or less.

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

The conductor material used in the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer includes one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium . The wiring layer may be a single metal layer or an alloy layer, and the alloy layer may be formed of, for example, two or more alloys (eg, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy) selected from the above-mentioned group. By. Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or . Chrome alloy, copper. Nickel alloy, copper. The alloy layer of titanium alloy is preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel. The alloy layer of chromium alloy is preferably a single metal layer of copper.

The thickness of the wiring layer depends on the desired design of the wiring board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, more preferably 10 μm to 20 μm, or 15 μm. In step (3), in the step of grinding or grinding the insulating layer to expose the wiring layer and connect the wiring layers between layers, the thicknesses of the interconnected interconnects and the unconnected interconnects are preferably different. The thickness of the wiring layer can be adjusted by repeating the aforementioned pattern formation. Among the wiring layers, the thickness of the thickest wiring layer (conductive pin) is determined according to the desired wiring board design, but is preferably 100 μm or less and 2 μm or more. In addition, the wiring connected by the layers can also be convex.

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

<Step (2)> Step (2) is a step of laminating the resin sheet of the present invention on the substrate with the wiring layer and thermally hardening to form an insulating layer by embedding the wiring layer in the resin composition layer. Specifically, the wiring layer of the substrate with wiring layer obtained in the aforementioned step (1) is laminated in a manner 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 form an insulating layer.

Lamination of the wiring layer and the resin sheet can be performed by, for example, heating and pressing the resin sheet on the wiring layer from the support side after removing the protective film of the resin sheet. As a member for heat-bonding the resin sheet to the wiring layer (hereinafter also referred to as "heat-bonding member"), for example, a heated metal plate (SUS lens plate) or a metal roll (SUS roll) is exemplified. Furthermore, it is preferable to press the resin sheet through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the unevenness of the surface of the wiring layer without pressing the thermocompression member directly against the resin sheet.

The lamination of the wiring layer and the resin sheet can also be performed by vacuum lamination after removing the protective film of the resin sheet. In the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, more preferably 80°C to 140°C, and the heating and pressing pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa The heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure with a pressure of 13 hPa or less.

After lamination, smoothing treatment of the laminated resin sheet is performed by pressing against the thermocompression member under normal pressure (at atmospheric pressure), for example, from the support side. The pressing conditions of the smoothing treatment may be the same as the heat pressing conditions of the above-mentioned lamination. Moreover, the lamination and smoothing process can also be performed continuously using the above-mentioned commercially available vacuum laminator.

After the resin composition layer is laminated on the wiring layer-attached substrate by embedding the wiring layer, the resin composition layer is thermally cured to form an insulating layer. For example, the thermal curing conditions of the resin composition layer also vary with the type of resin composition, but the curing temperature can be set in the range of 120°C to 240°C, and the curing time can be set in the range of 5 minutes to 120 minutes. Before the resin composition layer is thermally hardened, the resin composition layer may be preliminarily heated at a temperature lower than the hardening temperature.

The support of the resin sheet can be peeled off after the resin sheet is laminated on the substrate with a wiring layer and thermally hardened, or the support can be peeled off before the resin sheet is laminated on the substrate with a wiring layer. And the support body may be peeled off before the roughening process process mentioned later.

After thermosetting the resin composition layer to form the insulating layer, the surface of the insulating layer may be polished. The polishing method is not particularly limited, as long as it is polished by a conventional method, for example, the surface of the insulating layer can be polished using a flat polishing disc.

The surface roughness (Ra1) of the surface of the insulating layer after polishing is preferably at least 100 nm, more preferably at least 110 nm, and still more preferably at least 120 nm. The upper limit is preferably at most 450 nm, more preferably at most 400 nm, and still more preferably at most 350 nm. The surface roughness (Ra1) of the surface of the insulating layer after grinding can be measured according to the method described in the examples described later.

The maximum cross-sectional height (Rt1) of the roughness curve of the surface of the insulating layer after polishing is preferably 3000 nm or more, more preferably 3500 nm or more, and still more preferably 4000 nm or more. The upper limit is preferably at most 7000 nm, more preferably at most 6500 nm, and still more preferably at most 6000 nm. The maximum cross-sectional height (Rt1) of the roughness curve of the surface of the insulating layer after polishing can be measured according to the method described in the examples described later.

<Step (3)> Step (3) is a step of connecting wiring layers between layers. Specifically, it is a step of forming a through hole in an insulating layer, forming a conductor layer, and connecting the wiring layers between layers. And it is the step of grinding or grinding the insulating layer to expose the wiring layer and connecting the wiring layers between layers.

In the steps of forming a through hole in the insulating layer, forming a conductor layer and connecting the wiring layers between layers, the formation of the through hole is not particularly limited, but examples include laser irradiation, etching, mechanical drilling, etc., preferably by laser Irradiation proceeds. The laser irradiation can be performed using any laser processing machine using a carbon dioxide gas laser, a YAG laser, an excimer laser, or the like as a light source. Specifically, it is preferable to form a through hole through which the wiring layer is exposed by penetrating the support and the insulating layer by irradiating the laser from the surface side of the support of the resin sheet.

The laser irradiation conditions are not particularly limited, and the laser irradiation can be carried out by any appropriate steps according to a commonly used method according to the selected means.

The shape of the through hole, that is, the shape of the opening profile when viewed in the extending direction is not particularly limited, and is generally set to be circular (slightly circular).

After the through hole is formed, a so-called smear removal step, which is a step of removing the smear in the through hole, may also be performed. When the conductor layer is formed by the plating step, for example, a wet desmear treatment may be performed on the through holes, and when the conductor layer is formed by the sputtering step, a dry desmear treatment such as a plasma treatment step may be performed. Glue step. In addition, the desmear step may also serve as a roughening treatment step.

Before forming the conductor layer, the through hole and the insulating layer may also be roughened. The roughening process can be performed in a conventionally known order and condition. An example of the dry roughening treatment is plasma treatment, and an example of the wet roughening treatment is, for example, sequentially performing swelling treatment with a swelling liquid, coarsening treatment with an oxidizing agent, and neutralization with a neutralizing liquid. method of processing.

The surface roughness (Ra2) of the surface of the insulating layer after the roughening treatment is preferably at least 350 nm, more preferably at least 400 nm, still more preferably at least 450 nm. The upper limit is preferably at most 700 nm, more preferably at most 650 nm, still more preferably at most 600 nm. The surface roughness (Ra2) of the surface of the insulating layer after grinding can be measured according to the method described in the examples described later.

The maximum cross-sectional height (Rt2) of the roughness curve after the roughening treatment is preferably at least 7000 nm, more preferably at least 7500 nm, and still more preferably at least 8000 nm. The upper limit is preferably 12000 nm or less, more preferably 11000 nm or less, and still more preferably 10000 nm or less. The maximum cross-sectional height (Rt2) of the roughness curve of the surface of the insulating layer after grinding can be measured according to the method described in the examples described later.

After the via hole is formed, the conductor layer is formed. The conductor material constituting the conductor layer is not particularly limited, and the conductor layer can be formed by any preferred method known in the past, such as plating, sputtering, and vapor deposition, and more preferably, it is formed by plating. In a preferred embodiment, a conductor layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by conventional techniques such as a semi-additive method and a full-additive method. Moreover, when the support body of a resin sheet is a metal foil, the conductor layer which has a desired wiring pattern can be formed by the conventionally known technique, such as a subtraction method. The conductor layer may be a single-layer structure, or may be a multi-layer structure formed by laminating two or more single metal layers or alloy layers made of different kinds of metals or alloys.

Specifically, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer corresponding to a desired wiring pattern is formed. An electrolytic plating layer is formed by electrolytic plating on the exposed plating seed layer. At this time, at the same time as the formation of the electrolytic plating layer, the filled via hole is formed by burying the via hole by electrolytic plating. After the electrolytic plating layer is formed, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed. In addition, when forming a conductor layer, the dry film used for mask pattern formation is the same as the above-mentioned dry film.

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

In addition, the conductor layer may be formed by forming an electrolytic plating layer and a through hole without using a mask pattern after forming a plating seed layer, and then performing patterning by etching.

When using the step of grinding or grinding the insulating layer to expose the wiring layer and connect the wiring layers between layers, the grinding method or grinding method of the insulating layer is not particularly limited as long as the wiring layer can be exposed and the grinding or grinding surface is horizontal. Conventional grinding methods or grinding methods are applicable, such as chemical mechanical grinding methods using chemical mechanical grinding equipment, mechanical grinding methods such as polishing wheels, and plane grinding methods by rotating grinding stones. Similar to the steps of forming a through hole in the insulating layer, forming a conductor layer, and connecting the wiring layers between layers, the steps of smear removal treatment and roughening treatment can also be performed, and the conductor layer can also be formed. Moreover, not all the wiring layers need to be exposed, and a part of the wiring layers may be exposed.

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

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

As long as the terminal electrodes of the semiconductor chip are connected to the circuit wiring conductors of the circuit board, the bonding conditions are not particularly limited, and conventional conditions used in flip chip mounting of the semiconductor chip can be used. Furthermore, the semiconductor wafer and the circuit board may be joined via an insulating adhesive.

In a preferred embodiment, the semiconductor wafer is pressed against the circuit board. As the pressing conditions, for example, the pressing temperature can be set in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and the pressing time is 1 second to 1 second. The range of 60 seconds (preferably 5 seconds to 30 seconds).

Moreover, in another preferred embodiment, the semiconductor chip is reflowed to the circuit board for bonding. As a reflow condition, it can be set to the range of 120 degreeC - 300 degreeC, for example.

After bonding the semiconductor chip to the circuit substrate, for example, filling the semiconductor chip with a molded underfill material can also obtain a semiconductor chip package. The method of filling with molded underfill can be carried out by conventional methods. The resin composition or resin sheet of the present invention can also be used as a molded underfill material.

The second aspect of the semiconductor chip package of the present invention is, for example, a typical semiconductor chip package (fan-out WLP) shown in FIG. 1 . As shown in FIG. 1 , a typical semiconductor chip package (fan-out WLP) 100 is a semiconductor chip package in which the sealing layer 120 is made of 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, a rewiring formation layer (insulating layer) 130 on the surface opposite to the side covered by the sealing layer of the semiconductor chip 110, and a conductor layer (Rewiring layer) 140 , solder resist layer 150 and bump 160 . The manufacturing method of the semiconductor chip package includes the following steps: (A) the step of laminating the temporary fixing film on the substrate, (B) the step of temporarily fixing the semiconductor wafer 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 wafer, or coating the resin composition of the present invention on a semiconductor wafer, and forming a sealing layer by thermal curing, (D) the step of peeling the substrate from the semiconductor wafer and temporarily fixing the film, (E) the step of forming a rewiring formation layer (insulating layer) on the surface of the base material of the semiconductor wafer and the temporary fixing film, (F) the step of forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer), and (G) A step of forming a solder resist layer on the conductor layer. Furthermore, the manufacturing method of a semiconductor chip package may include (H) the step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and singulation.

<Step (A)> Step (A) is a step of laminating a temporary fixing film on the substrate. 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 the step (2) in the manufacturing method of the circuit board, and the preferred range is also the same.

The material used for the base material is not particularly limited. Examples of substrates are silicon wafers; glass wafers; glass substrates; metal substrates of copper, titanium, stainless steel, cold rolled steel plate (SPCC), etc.; FR-4 substrate); a substrate made of bismaleimide triazine resin (BT resin), etc.

The temporary fixing film can be peeled off from the semiconductor wafer in the later-mentioned step (D), and the material is not particularly limited as long as the semiconductor wafer can be temporarily fixed. A commercial item can be used for the temporary fixation film. Examples of commercially available products include RIVA ALPHA manufactured by Nitto Denko Corporation.

<Step (B)> Step (B) is a step of temporarily fixing the semiconductor wafer on the temporary fixing film. The temporary fixation of the semiconductor wafer can be performed using conventional devices such as flip chip bonders, die bonders, and the like. The layout and number of arrangements of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the number of production of the intended semiconductor package, etc. For example, a matrix of plural rows and columns can be arranged and temporarily fixed.

<Step (C)> Step (C) is a step of laminating the resin composition layer of the resin sheet of the present invention on the semiconductor wafer, or coating the resin composition of the present invention on the semiconductor wafer, and thermally hardening to form a sealing layer. In the step (C), the resin composition layer of the resin sheet of the present invention is preferably laminated on the semiconductor wafer, and thermally cured to form a sealing layer.

The lamination of the semiconductor wafer and the resin sheet can be performed by, for example, heating and pressing the resin sheet to the semiconductor wafer from the support side after removing the protective film of the resin sheet. Examples of members for thermally pressing a resin sheet to a semiconductor wafer (hereinafter also referred to as "thermal pressing members") include heated metal plates (SUS lens plates, etc.), metal rolls (SUS rolls), and the like. Furthermore, it is preferable that the thermocompression member is not directly pressed against the resin sheet, but is pressed via an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the unevenness of the semiconductor surface.

In addition, the lamination of the semiconductor wafer and the resin sheet may be performed by vacuum lamination after removing the protective film of the resin sheet. The lamination conditions of the vacuum lamination method are the same as the lamination conditions of the wiring layer and the resin sheet in step (2) in the manufacturing method of the circuit board, and the preferable range is also the same.

The support of the resin sheet can be peeled off after the resin sheet is laminated on the semiconductor wafer and thermally hardened, or the support can be peeled off before the resin sheet is laminated on the semiconductor wafer.

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

<Step (D)> Step (D) is a step of peeling the substrate from the semiconductor wafer and temporarily fixing the film. The peeling method can be appropriately changed according to the material of the temporary fixing film. For example, the temporary fixing film is heated, foamed (or expanded) and peeled off, and ultraviolet rays are irradiated from the substrate side to reduce the adhesive force of the temporary fixing film and peel it off. method etc.

In the method of heating, foaming (or expanding) and peeling the temporarily fixed film, the heating conditions are usually 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. Moreover, in the method of irradiating ultraviolet rays from the base material side to reduce the adhesive force of the temporarily fixed film and peeling, the irradiation amount of the ultraviolet rays is usually 10 mJ/cm ² to 1000 mJ/cm ² .

<Step (E)> The step (E) is a step of forming a rewiring formation layer (insulating layer) on the surface of the substrate of the semiconductor wafer and the temporary fixing film.

The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties when the rewiring formation layer (insulating layer) is formed, but from the viewpoint of the ease of manufacture of the semiconductor chip package, a photosensitive resin, a thermal Hardening resin. As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention can also be used.

After the rewiring formation layer (insulating layer) is formed, a through hole may be formed in the rewiring formation layer (insulating layer) for interlayer connection between the semiconductor wafer and the conductor layer described later.

In forming the through hole, when the material for forming the rewiring formation layer (insulating layer) is a photosensitive resin, first, the surface of the rewiring formation layer (insulating layer) is irradiated with active energy rays through a mask pattern, so that the rewiring layer in the irradiated part is irradiated with active energy rays. Light hardening.

Examples of active energy rays include ultraviolet rays, visible light, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. 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 adhered to the rewiring formation layer (insulating layer) and exposed, and a parallel light ray is used without adhering the mask pattern to the rewiring formation layer (insulating layer) Any of the non-contact exposure methods for exposure.

Next, the rewiring formation layer (insulating layer) is developed to remove the unexposed portion, thereby forming a through hole. The development can be applied to either wet development or dry development. As the developer used in wet development, a conventional developer can be used.

Examples of the developing method include a dipping method, a liquid coating method, a spraying method, a brush coating method, and an extrusion coating method, and the liquid coating method is preferred from the viewpoint of resolution.

When the material for forming the rewiring formation layer (insulating layer) is a thermosetting resin, the formation of the through hole is not particularly limited, and examples include laser irradiation, etching, mechanical drilling, etc., preferably by laser irradiation. The laser irradiation can be performed using any laser processing machine using carbon dioxide gas laser, UV-YAG laser, excimer laser, etc. as a light source.

The laser irradiation conditions are not particularly limited, and the laser irradiation can be carried out by any preferred steps of common methods according to the selected means.

The shape of the through hole, that is, the shape of the opening profile when viewed in the extending direction is not particularly limited, and is generally set to be circular (slightly circular). The hole top diameter of the through hole (the opening diameter of the rewiring layer (insulating layer) surface) is preferably 50 μm or less, more preferably 30 μm or less, and still more preferably 20 μm or less. The lower limit is not particularly limited, but is preferably at least 10 μm, more preferably at least 15 μm, and still more preferably at least 20 μm.

<Step (F)> Step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer). The method of forming the conductor layer on the rewiring formation layer (insulation layer) is the same as the method of forming the conductor layer after forming the through hole in the insulating layer in step (3) of the manufacturing method of the circuit board, and the preferred range is also the same. Moreover, the step (E) and the step (F) may be repeatedly performed, and the conductor layer (rewiring layer) and the rewiring formation layer (insulating layer) may be alternately laminated (build-up layer).

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

The material for forming the solder resist layer is not particularly limited as long as it has insulating properties at the time of the solder resist layer, but is preferably a photosensitive resin or a thermosetting resin from the viewpoint of the ease of manufacture of the semiconductor chip package. As the thermosetting resin, a resin composition having the same composition as the resin composition for forming the resin sheet of the present invention can also be used.

In addition, in step (G), bump processing for forming bumps may be performed as required. Bumping can be performed by conventional methods such as solder balls, solder plating, and the like. In addition, the formation of through holes in the bump processing can be performed in the same manner as in step (E).

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

The method of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages is not particularly limited, and a conventional method can be used.

The third aspect of the semiconductor chip package of the present invention is to manufacture, for example, a rewiring formation layer (insulating layer) in a semiconductor chip package (fan-out WLP) as shown in FIG. 1 using the resin composition or resin sheet of the present invention. 130. The semiconductor chip package of the solder resist layer 150.

[semiconductor device] As the semiconductor device for mounting the semiconductor chip package of the present invention, it is exemplified for electrical products (such as computers, mobile phones, smart phones, tablet devices, wearable devices, digital cameras, medical equipment and televisions, etc.) and carriers ( For example, various semiconductor devices such as locomotives, automobiles, trains, ships, and airplanes. [Example]

The present invention is specifically described below by means of examples, but the present invention is not limited to these examples. In addition, in the following description, unless otherwise indicated, "part" and "%" mean "mass part" and "mass %", respectively.

<Preparation of samples for measuring peel strength and surface roughness (Ra value) of conductor layers> (1) Substrate treatment of inner layer circuit substrate The glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.3mm, R5715ES manufactured by PANASONIC) on both sides of the glass cloth substrate with inner layer circuit formed is immersed in CZ8100 manufactured by MERCK Corporation for copper surface roughening treatment .

(2) Lamination of resin sheets PET film ("LUMIRROR R80" manufactured by Toray Corporation) subjected to mold release treatment with an alkyd resin-based mold release agent ("AL-5" manufactured by LINTEC Corporation), thickness 38μm, softening point 130°C, hereinafter sometimes referred to as "" On the mold release PET”), the resin varnishes produced in the Examples and Comparative Examples were coated with a die nozzle applicator so that the thickness of the resin composition layer after drying became 200 μm, at 80°C to 120°C (average 100°C) A resin sheet was obtained by drying for 10 minutes. The resin sheet was laminated using a batch vacuum press laminator (manufactured by Meiki Co., Ltd., MVLP-500) so that the resin composition layer was in contact with both surfaces of the inner-layer circuit board. The lamination was performed by reducing the pressure for 30 seconds, setting the air pressure to 13 hPa or less, and then pressing at 100° C. for 30 seconds at a pressure of 0.74 MPa.

(3) Hardening of the resin composition layer The mold release PET was peeled off from the laminated resin sheet, and the resin composition layer was cured to form an insulating layer under curing conditions of 180° C. and 30 minutes.

(4) Grinding of insulating layer The insulating layer of the inner-layer circuit board on which the insulating layer was formed was ground and cut with a flat polishing pad under the following conditions. The inner layer circuit board after the insulating layer was ground and cut was used as the evaluation board A. Grinding and cutting conditions: The peripheral speed of the grinding stone is 500m/min, the machine speed is 13m/min, the cutting amount at one time is 3μm, the total cutting thickness is 50μm, and the grinding stone number is #1000

(5) Roughening treatment The inner layer circuit substrate with the ground and cut insulating layer was immersed in Sweeling Dip Securiganth P containing diethylene glycol monobutyl ether made by Japan ATOTECH Co., Ltd. as a swelling solution at 60°C for 5 minutes, Next, it was immersed in Concentrate Compact P (aqueous solution of KMnO ₄ : 60 g/L, NaOH: 40 g/L) manufactured by Japan ATOTECH Co., Ltd. as a roughening solution at 80° C. for 15 minutes, and finally it was immersed in ATOTECH Co., Ltd. as a neutralizing solution. Immersion in Reduction Solution Securiganth P at 40°C for 5 minutes.

(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 a solution for electroless plating containing PdCl ₂ , and then immersed in an electroless copper plating solution. After heating at 150° C. for 30 minutes to perform annealing treatment, an etching resist was formed, and after patterning by etching, copper sulfate electroplating was performed to form a plated conductor layer with a thickness of 30±5 μm. Next, annealing treatment was performed at 180° C. for 60 minutes. This circuit board was used as the evaluation board B.

<The surface roughness of the insulating layer surface after grinding and cutting (Ra1), the maximum section height of the roughness curve of the insulating layer surface after grinding and cutting (Rt1), the surface roughness of the insulating layer surface after roughening treatment (Ra2), Determination of the maximum section height (Rt2) of the roughness curve after roughening treatment> Using a non-contact surface roughness meter (WYKO NT3300 manufactured by Veeco Instruments), the surface of the insulating layer of the evaluation substrate A was measured in the VSI contact mode with a 50x lens and the measurement range was set to 121 μm×92 μm, and the surface of the insulating layer after grinding and cutting was obtained. The surface roughness of the insulating layer surface and the maximum profile height of the roughness curve. Ra1 and Rt1 were measured by obtaining the average value of 10 points, respectively.

Ra2 and Rt2 were measured similarly to the insulating layer surface of the evaluation board A by the measurement of the insulating layer surface after roughening process in the board|substrate A for evaluation.

<Measurement and evaluation of peel strength with conductor layer> Cut out a 10mm wide and 100mm long part of the conductor layer of the evaluation substrate B, peel off one end of the conductor layer and clamp it with a jig, and measure the load when peeling off in the vertical direction at a speed of 50mm/min at room temperature (kgf/cm). When the peel strength was less than 0.40 kgf/cm, it was evaluated as ×, when it was 0.40 kgf/cm or more and less than 0.45 kgf/cm, it was evaluated as Δ, and when it was 0.45 kgf/cm or more, it was evaluated as ○.

<Evaluation of Resin Residue at Bottom of Via Hole (Laser Via Reliability)> (1) Substrate treatment of inner layer circuit substrate The glass cloth base material epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.3mm, R1515F manufactured by PANASONIC) on both sides of the glass cloth substrate with inner layer circuit formed is dipped in CZ8100 manufactured by MERCK Corporation for copper surface roughening treatment .

(2) Lamination of resin sheets On the mold release PET, the resin varnishes prepared in the examples and the comparative examples were coated with a die nozzle applicator so that the thickness of the resin composition layer after drying became 30 μm, and dried at 80°C to 120°C (average 100°C) Resin flakes were obtained in 10 minutes. The resin sheet was laminated using a batch vacuum pressure laminator (manufactured by Meiki Co., Ltd., MVLP-500) so that the resin composition layer was in contact with both surfaces of the inner-layer circuit board. The lamination was performed by reducing the pressure for 30 seconds, setting the air pressure to 13 kPa or less, and then pressing at 100° C. for 30 seconds at a pressure of 0.74 MPa.

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

(4) A CO ₂ laser processing machine (“LC-2E21B/1C” manufactured by Hitachi VIA MECHANICS Co., Ltd.) was used to form the through hole, with a mask diameter of 1.60 mm, a focus deviation value of 0.050, a pulse width of 25 μs, a power of 0.66 W, and an aperture of 0.66 W. 13. The number of shots is 2, the condition of the burst mode, the insulating layer is perforated to form a through hole. The top diameter (diameter) of the through hole on the surface of the insulating layer is 50 μm. After the through hole is formed, the mold release PET is peeled off.

(5) Roughening treatment The circuit board on which the insulating layer was formed was immersed in a swelling solution (“Sweeling Dip Securiganth P” manufactured by ATOTECH, an aqueous solution containing diethylene glycol monobutyl ether and sodium hydroxide) at 60°C 5 minutes, followed by immersion in a roughening solution (“Concentrate Compact P” manufactured by ATOTECH, Japan, KMnO ₄ : 60g/L, NaOH: 40g/L aqueous solution) at 80°C for 15 minutes, and finally in a neutralizing solution (Japan After being immersed in "Reduction Solution Securiganth P" manufactured by ATOTECH, aqueous sulfuric acid solution) at 40°C for 5 minutes, it was dried at 80°C for 30 minutes.

(6) Evaluation of Resin Residues at the Bottom of Vias (Laser Via Reliability) The periphery of the bottom of the through hole was observed with a scanning electron microscope (SEM), and the maximum smear length from the wall surface of the bottom of the through hole was determined from the obtained image. The evaluation criteria are shown below. Evaluation benchmark: ○: The maximum slag length is less than 3μm ×: The maximum slag length is 3 μm or more

<Measurement of elastic modulus and measurement of 1% weight loss temperature> (1) Preparation of hardened product for evaluation On the untreated surface of the release agent-treated PET film ("501010" manufactured by LINTEC Corporation, thickness 38 μm, 240 mm square), overlap the glass cloth epoxy resin laminate on both sides ("R5715ES" manufactured by PANASONIC Corporation, Thickness 0.7mm, 255mm square) and the four sides are fixed with polyimide adhesive tape (width 10mm) (hereinafter sometimes referred to as "fixed PET film").

On the mold release treatment surface of the above-mentioned "fixed PET film", the resin varnishes produced in the Examples and Comparative Examples were applied with a die nozzle applicator in such a way that the thickness of the resin composition layer after drying was 40 μm, and the temperature was 80 ℃ ~ A resin sheet was obtained by drying at 120°C (average 100°C) for 10 minutes.

Next, after putting into an oven at 180° C., the resin composition layer was thermally cured under the curing conditions of 180° C. and 90 minutes.

After thermal curing, peel off the polyimide adhesive tape, remove the cured product from the epoxy resin laminate on both sides of the glass cloth substrate, and then peel off the PET film ("501010" manufactured by LINTEC) to obtain a sheet-like cured product . The obtained hardened product is called "hardened product for evaluation".

(2) Determination of elastic modulus A dumbbell-shaped No. 1 shape was cut out from the cured product for evaluation to obtain a test piece. This test piece was subjected to a tensile strength test using a tensile tester "RTC-1250A" manufactured by ORIENTEC, and the elastic modulus at 23°C was determined. The measurement was carried out in accordance with JIS K7127. This operation was carried out 3 times and the average values are shown in the table below.

(3) Measurement of 1% weight loss temperature (heat resistance evaluation) Thermogravimetric measurement when the cured product for evaluation was heated from 25°C to 400°C at a temperature increase rate of 10°C/min using a differential thermogravimetric measuring apparatus (TG/DTA6200, manufactured by SEIKO INSTRUMENTS Co., Ltd.) while blowing nitrogen gas at 250 ml/min. , find the 1% weight loss temperature. When the 1% weight loss temperature was 350°C or more, it was evaluated as "○", and when it was less than 350°C, it was evaluated as "x".

[Synthesis Example 1] 69 g of bifunctional hydroxyl-terminated polybutadiene (G-3000, manufactured by Nippon Soda Co., Ltd., number average molecular weight=3000, hydroxyl equivalent=1800 g/eq) and IPSOL 150 (aromatic hydrocarbon) were mixed in a reaction vessel A mixed solvent: 40 g of Idemitsu Petrochemical Co., Ltd., 0.005 g of dibutyltin laurate, and uniformly dissolved. After the temperature was raised to 50° C., isophorone diisocyanate (manufactured by EBONIC DEGUSSA JAPAN, IPDI, isocyanate group equivalent = 113 g/eq) was added with stirring and reacted for about 3 hours. Next, after cooling the reactant to room temperature, 23 g of cresol novolak resin (KA-1160, manufactured by DIC Corporation, hydroxyl equivalent = 117 g/eq) and 60 g of ethylene glycol acetate (manufactured by DAICEL Corporation) were added thereto. , the temperature was raised to 80°C while 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. It was confirmed that the disappearance of the NCO peak was regarded as the end of the reaction, and the reactant was cooled to room temperature and filtered with a 100-mesh filter cloth to obtain the component (A) of Synthesis Example 1 (nonvolatile component 50 having a butadiene structure and a phenolic hydroxyl group) quality%). The number average molecular weight was 5500.

[Synthesis Example 2] In a flask equipped with a stirring device, a thermometer and a condenser, 292.09 g of ethylene glycol acetate and 292.09 g of SOLVESSO 150 (aromatic solvent, manufactured by EXXON MOBIL) were charged as solvents, and diphenylmethane 100.1 g (0.4 mol) of isocyanate and 426.6 g (0.2 mol) of polybutadiene glycol (hydroxyl value 52.6KOH-mg/g, molecular weight 2133) were reacted at 70°C for 4 hours. Then, 195.9 g (0.2 mol) of nonylphenol novolac resin (hydroxyl equivalent 229.4 g/eq, average 4.27 functional groups, average calculated molecular weight 979.5 g/mol) and 41.0 g of ethylene glycol bis-pyromellitic anhydride were fed (0.1 mol), the temperature was raised to 150° C. over 2 hours, and the reaction was performed for 12 hours to obtain (A) component (55.2 mass % of nonvolatile content) of Synthesis Example 2 having a butadiene structure and a phenolic hydroxyl group.

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

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

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

[Example 4] Mixed liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/ eq) 10 parts, naphthol type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent about 330) 20 parts, glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy resin Equivalent weight: 90~105g/eq) 10 parts, hardening accelerator (“1B2PZ” manufactured by Shikoku Chemical Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, (A) component of Synthesis Example 1 (solid content 50 %, number average molecular weight: 5500) 300 parts, biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide equivalent weight: 275g/eq, no MEK/toluene mixed solution with 70% volatile content) 28.5 parts, carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide group equivalent 216, non-volatile content 50 mass% toluene solution) 4 parts, SO-C2 (950 parts of spherical silica (made by Admatechs, average particle size 0.5 μm) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) and methyl ethyl acetate 60 parts of base ketones were uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[Example 5] Mixed liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/ eq) 10 parts, naphthol type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent about 330) 12 parts, glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy resin Equivalent weight: 90~105g/eq) 10 parts, hardening accelerator (“1B2PZ” manufactured by Shikoku Chemical Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, (A) component of Synthesis Example 1 (solid content 50 %, number average molecular weight: 5500) 300 parts, biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide equivalent weight: 275g/eq, no 70% MEK/toluene mixed solution of volatile content) 40 parts, carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide group equivalent 216, non-volatile content 50% by mass toluene solution) 14 parts, SO-C2 (Spherical silica (made by Admatechs Co., Ltd., average particle size 0.5 μm) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) 950 parts and methyl ethyl acetate 60 parts of base ketones were uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

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

[Comparative Example 1] Mixed liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/ eq) 10 parts, naphthol-type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent of about 330) 10 parts, resin containing polyalkylene oxide structure ("XY7400" manufactured by Mitsubishi Chemical Corporation, ring Oxygen equivalent: 440g/eq) 10 parts, Glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90~105g/eq) 10 parts, Hardening accelerator ("1B2PZ manufactured by Shikoku Chemical Corporation" ”, 1 part of 1-benzyl-2-phenylimidazole), 272 parts of (A) component (solid content 55.2%) of Synthesis Example 2, active ester-based hardener (“HPC-8000-65T” manufactured by DIC Corporation, Active group equivalent of about 225, toluene solution of 65% by mass of non-volatile content) 31 parts, SO-C4 (Spherical silica (Admatechs) surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) Company made, 960 parts of average particle size 1 μm)) and 90 parts of methyl ethyl ketone were uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[Comparative Example 2] Mixed liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/ eq) 45 parts, naphthalene type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent about 330) 100 parts, naphthol type epoxy resin ("HP4710" manufactured by DIC Corporation, epoxy equivalent 160~ 180g/eq) 32 parts, glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 90~105g/eq) 35 parts, hardening accelerator ("1B2PZ" manufactured by Shikoku Chemical Corporation, 1 -Benzyl-2-phenylimidazole) 1 part, active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 225, toluene solution of 65% by mass of non-volatile content) 35.4 parts, SO -C4 (Spherical silica surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Admatechs, Inc., average particle size: 1 μm)) 1340 parts, biphenyl aralkyl type maleic Imide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide group equivalent: 275g/eq, MEK/toluene mixed solution of 70% non-volatile content) 28.5 parts, carbodiimide Resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., 216 carbodiimide group equivalents, toluene solution of 50% by mass of non-volatile content) and 250 parts of methyl ethyl ketone were uniformly dispersed with a high-speed rotary mixer, Make resin varnish.

[Comparative Example 3] Mixed liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/ eq) 14 parts, naphthol type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent about 330) 20 parts, glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy resin Equivalent weight: 90~105g/eq) 13 parts, hardening accelerator (“1B2PZ” manufactured by Shikoku Chemical Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, (A) component of Synthesis Example 1 (solid content 50 %, number average molecular weight: 5500) 300 parts, biphenyl aralkyl maleimide resin ("MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd., maleimide equivalent weight: 275g/eq, no MEK/toluene mixed solution with 70% volatile content) 28.5 parts, SO-C2 (Spherical silica (manufactured by Admatechs, average particle size) surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 950 parts of 0.5 μm diameter)) and 120 parts of methyl ethyl ketone were uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

[Comparative Example 4] Mixed liquid epoxy resin ("ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., 1:1 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (mass ratio), epoxy equivalent: 169g/ eq) 20 parts, naphthol type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent about 330) 20 parts, glycidylamine type epoxy resin ("630LSD" manufactured by Mitsubishi Chemical Corporation, epoxy resin Equivalent: 90~105g/eq) 20 parts, hardening accelerator (“1B2PZ” manufactured by Shikoku Chemical Co., Ltd., 1-benzyl-2-phenylimidazole) 1 part, (A) component of Synthesis Example 1 (solid content 50 %, number average molecular weight: 5500) 300 parts, carbodiimide resin ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., carbodiimide group equivalent 216, toluene solution of 50% by mass of nonvolatile content) 14 parts, SO-C2 (Spherical silica (manufactured by Admatechs, average particle size 0.5 μm) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.)) 950 parts and methyl ethyl ketone 120 Parts, uniformly dispersed with a high-speed rotary mixer to make resin varnish.

The main abbreviations in the following table are as follows. Synthesis Example 1: Component (A) of Synthesis Example 1 Synthesis Example 2: Component (A) of Synthesis Example 2 YX7400: Resin containing polyalkoxy structure, manufactured by Mitsubishi Chemical Corporation ZX1059: 1:1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin (mass ratio), epoxy equivalent: 169g/eq, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. 630LSD: Glycidylamine type epoxy resin, epoxy equivalent: 90~105g/eq, manufactured by Mitsubishi Chemical Corporation ESN475V: Naphthol-type epoxy resin, epoxy equivalent of about 330, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. 157S70: Bisphenol A novolac epoxy resin, epoxy equivalent 210 g/eq, manufactured by Mitsubishi Chemical Corporation HP-4710: Naphthalene type epoxy resin, epoxy equivalent 160~180g/eq, manufactured by DIC Corporation V-03: Carbodiimide resin, carbodiimide group equivalent weight 216, toluene solution of 50% by mass of non-volatile content, manufactured by Nisshinbo Chemical Co., Ltd. MIR-3000-70MT: biphenyl aralkyl maleimide resin, maleimide group equivalent: 275g/eq, MEK/toluene mixed solution of 70% non-volatile content, Nippon Kayaku Co., Ltd. SO-C4: Spherical silica surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Admatechs, Inc., average particle size: 1 μm) SO-C2: Spherical silica surface-treated with an aminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Admatechs, Inc., with an average particle size of 0.5 μm) 1B2PZ: Hardening accelerator, 1-benzyl-2-phenylimidazole, manufactured by Shikoku Chemical Co., Ltd. HPC-8000-65T: Active ester-based hardener, active group equivalent of about 225, toluene solution of 65% by mass of non-volatile content, manufactured by DIC Corporation

From the results of Examples 1 to 6, the elastic modulus of the insulating layer formed from the resin composition containing the components (A) to (E) was 17 GPa or less, which was low, so that the occurrence of warpage was suppressed. In addition, it was found that the peel strength was also preferably 0.4 kgf/cm or more, and the adhesion to the conductor layer was excellent. Furthermore, the 1% weight reduction temperature is sufficiently high, so the heat resistance is excellent, and the resin residue at the bottom of the via hole is also suppressed, so the reliability of the laser via hole is also excellent. Furthermore, it can be seen that the surface roughness of the surface of the insulating layer after grinding and cutting (Ra1), the maximum cross-sectional height of the roughness curve of the surface of the insulating layer after grinding and cutting (Rt1), and the surface roughness of the surface of the insulating layer after roughening treatment ( Ra2) and the maximum cross-sectional height (Rt2) of the roughness curve after roughening treatment are also excellent. On the other hand, it can be seen that Comparative Examples 1, 3 to 4 that do not contain (C) and/or (D) components have peel strength, 1% weight reduction temperature, and resin residue at the bottom of the through hole compared to Examples 1 to 6. Either is worse. Moreover, the comparative example 2 which does not contain (A) component, compared with Examples 1-6, the elastic modulus was high, and the peeling strength and the resin residue at the bottom of a through-hole were inferior. In addition, in Comparative Example 2, Ra2 and Rt2 were not measured. In addition, even when the component (F) was not contained, it was confirmed that the results were returned to the same results as those of the above-mentioned Examples, although the degree was poor.

100: Semiconductor Chip Packaging 110: Semiconductor wafer 120: sealing layer 130: Rewiring formation layer (insulating layer) 140: Conductor layer (rewiring layer) 150: Solder resist layer 160: bump

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

Claims (19)

A resin composition comprising: (A) Selected from resins having a number average molecular weight (Mn) of 1,000 to 1,000,000 and a glass transition temperature (Tg) of 25°C or lower, and resins having a number average molecular weight (Mn) of 1,000 to 1,000,000 and liquid at 25°C 1 or more resins, (B) epoxy resins having an aromatic structure, (C) a carbodiimide compound, (D) biphenyl aralkyl type resins (except those equivalent to component (B)), and (E) Inorganic filler. The resin composition according to claim 1, wherein the elastic modulus of the cured product at 23°C after thermally hardening the resin composition at 180°C for 90 minutes is 17 GPa or less. The resin composition of claim 1, wherein the content of the (A) component is 30 to 85 mass % when the non-volatile content of the resin composition excluding the (E) component is 100 mass %. The resin composition according to claim 1, wherein the content of the component (E) is 60 mass % or more when the non-volatile matter in the resin composition is 100 mass %. The resin composition of claim 1, wherein the component (A) is selected from resins with a number average molecular weight (Mn) of 5,000 to 900,000 and a glass transition temperature of 25°C or less, and a number average molecular weight (Mn) of 5,000 to 900,000 and a 25°C is one or more of liquid resins. The resin composition according to claim 1, wherein the component (A) has a polybutadiene structure. The resin composition of claim 1, wherein the component (A) has one or more functional groups selected from the group consisting of a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. The resin composition according to claim 1, wherein the component (A) has an imide structure. The resin composition according to claim 1, wherein the component (A) has a phenolic hydroxyl group. The resin composition according to claim 1, wherein the component (A) has a polybutadiene structure and a phenolic hydroxyl group. The resin composition according to claim 1, wherein the component (D) has a maleimide group in the molecule. The resin composition according to claim 5, wherein the component (D) has a maleimide group in the molecule. The resin composition according to claim 6, wherein the component (D) has a maleimide group in the molecule. The resin composition of claim 1, which is a resin composition for an insulating layer of a semiconductor chip package. A resin sheet having a support body and a resin composition layer comprising the resin composition according to any one of claims 1 to 14 provided on the support body. The resin sheet of claim 15, which is a resin sheet for an insulating layer of a semiconductor chip package. A circuit board comprising an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 14. A semiconductor chip package comprising the circuit substrate of claim 17 and a semiconductor chip mounted on the circuit substrate. A semiconductor chip package comprising a semiconductor chip sealed by the resin composition as claimed in any one of claims 1 to 14 or the resin sheet as claimed in claim 15.

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