JP2017179012A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having suppressed generation of warpage and excellent in peel strength and heat resistance, a resin sheet, a circuit board and a semiconductor chip package.SOLUTION: There is provided a resin composition containing (a) an elastomer, (b) an epoxy resin, (c) an inorganic filler and (d) a dihydroxynaphthalene compound, the content of (a) component is 30 mass% to 85 mass% based on 100 mass% of a nonvolatile component of the resin composition excluding (c) component, the content of (c) component is 50 mass% to 95 mass% based on 100 mass% of a nonvolatile component of the resin composition and elastic modulus at 23°C of a thermal cured article after thermally curing the resin composition at 180°C for 1 hour is 18 GPa or less.SELECTED DRAWING: None

Description

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

  In recent years, the demand for small, high-performance electronic devices such as smartphones and tablet PCs has increased, and accordingly, the semiconductor package insulating material (insulating layer) used in these small electronic devices is required to have higher functionality. ing.

  Such an insulating layer is known to be formed by curing a resin composition (see, for example, Patent Document 1).

JP2015-82535A

  By the way, since an insulating layer used for a wafer level chip size package or a wiring board having an embedded wiring layer is required to suppress warping and peel strength when forming the insulating layer, The use of a material in which a flexible resin is highly filled with an inorganic filler has been studied.

  However, the current situation is that the required warpage suppression and peel strength have not been met.

  The present invention has been made in order to solve the above-mentioned problems, the occurrence of warpage is suppressed, a resin composition excellent in peel strength and heat resistance, a resin sheet using the resin composition, a circuit board, and It is to provide a semiconductor chip package.

（式（１）中、Ｒ^１は、置換基を有していてもよい炭素原子数１〜６のアルキル基、置換基を有していてもよい炭素原子数１〜６のアルコキシ基、又は置換基を有していてもよい炭素原子数６〜１０のアリール基を表し、ｎは０〜４の整数を表す。Ｒ^１が複数存在する場合、それぞれのＲ^１は同一であってもよく、互いに異なっていてもよい。Ｒ^２は、単結合又は置換基を有していてもよい２価の連結基を表し、ｍは１〜６の整数を表す。Ｒ^２が複数存在する場合、それぞれのＲ^２は同一であってもよく、互いに異なっていてもよい。）
［３］ （ｄ）成分が、下記式（２）で表される、［１］又は［２］に記載の樹脂組成物。

（式（２）中、Ｒ^１１は、置換基を有していてもよい炭素原子数１〜６のアルキル基、置換基を有していてもよい炭素原子数１〜６のアルコキシ基、又は置換基を有していてもよい炭素原子数６〜１０のアリール基を表し、ｎ１は０〜６の整数を表す。Ｒ^１１が複数存在する場合、それぞれのＲ^１１は同一であってもよく、互いに異なっていてもよい。）
［４］ （ａ）成分が、ブタジエン構造単位、ポリシロキサン構造単位、（メタ）アクリレート構造単位、アルキレン構造単位、アルキレンオキシ構造単位、イソプレン構造単位、イソブチレン構造単位、およびポリカーボネート構造単位から選択される１種以上の構造単位を有する、［１］〜［３］のいずれかに記載の樹脂組成物。
［５］ （ａ）成分が、ガラス転移温度が２５℃以下の樹脂、および２５℃で液状である樹脂から選択される１種以上である、［１］〜［４］のいずれかに記載の樹脂組成物。
［６］ （ａ）成分が、（ｂ）成分と反応し得る官能基を有する、［１］〜［５］のいずれかに記載の樹脂組成物。
［７］ （ａ）成分が、イミド構造を有する、［１］〜［６］のいずれかに記載の樹脂組成物。
［８］ （ａ）成分が、フェノール性水酸基を有する、［１］〜［７］のいずれかに記載の樹脂組成物。
［９］ 支持体と、該支持体上に設けられた、［１］〜［８］のいずれかに記載の樹脂組成物を含む樹脂組成物層と、を有する樹脂シート。
［１０］ 半導体チップが搭載される面が、［１］〜［８］のいずれかに記載の樹脂組成物の硬化物により形成された絶縁層を含む、回路基板。
［１１］ ［１０］に記載の回路基板上に、半導体チップが搭載された、半導体チップパッケージ。 That is, the present invention includes the following contents.
[1] A resin composition comprising (a) an elastomer, (b) an epoxy resin having an aromatic structure, (c) an inorganic filler, and (d) a dihydroxynaphthalene compound,
When the nonvolatile component of the resin composition excluding the component (c) is 100% by mass, the content of the component (a) is 30% by mass to 85% by mass,
(C) When content of a component makes the non-volatile component of a resin composition 100 mass%, it is 50 mass%-95 mass%,
The resin composition whose elastic modulus in 23 degreeC of the thermosetting material which heat-cured the resin composition at 180 degreeC for 1 hour is 18 GPa or less.
[2] The resin composition according to [1], wherein the component (d) is represented by the following formula (1).

(In Formula (1), R ¹ is an alkyl group having 1 to 6 carbon atoms which may have a substituent, an alkoxy group having 1 to 6 carbon atoms which may have a substituent, or Represents an optionally substituted aryl group having 6 to 10 carbon atoms, and n represents an integer of 0 to 4. When a plurality of R ¹ are present, each R ¹ may be the same. R ² represents a single bond or a divalent linking group which may have a substituent, m represents an integer of 1 to 6. When a plurality of R ² are present, Each R ² may be the same or different from each other.
[3] The resin composition according to [1] or [2], wherein the component (d) is represented by the following formula (2).

(In Formula (2), R ¹¹ is an alkyl group having 1 to 6 carbon atoms which may have a substituent, an alkoxy group having 1 to 6 carbon atoms which may have a substituent, or Represents an aryl group having 6 to 10 carbon atoms which may have a substituent, and n1 represents an integer of 0 to 6. When a plurality of R ¹¹ are present, each R ¹¹ may be the same. May be different from each other.)
[4] The component (a) is selected from a butadiene structural unit, a polysiloxane structural unit, a (meth) acrylate structural unit, an alkylene structural unit, an alkyleneoxy structural unit, an isoprene structural unit, an isobutylene structural unit, and a polycarbonate structural unit. The resin composition according to any one of [1] to [3], which has one or more structural units.
[5] The component (a) according to any one of [1] to [4], wherein the component (a) is at least one selected from a resin having a glass transition temperature of 25 ° C. or lower and a resin that is liquid at 25 ° C. Resin composition.
[6] The resin composition according to any one of [1] to [5], wherein the component (a) has a functional group capable of reacting with the component (b).
[7] The resin composition according to any one of [1] to [6], wherein the component (a) has an imide structure.
[8] The resin composition according to any one of [1] to [7], wherein the component (a) has a phenolic hydroxyl group.
[9] A resin sheet comprising a support and a resin composition layer including the resin composition according to any one of [1] to [8] provided on the support.
[10] A circuit board on which a surface on which a semiconductor chip is mounted includes an insulating layer formed of a cured product of the resin composition according to any one of [1] to [8].
[11] A semiconductor chip package in which a semiconductor chip is mounted on the circuit board according to [10].

  ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of curvature is suppressed and the resin sheet, circuit board, and semiconductor chip package using the resin composition which is excellent in peel strength and heat resistance, and this resin composition can be provided.

FIG. 1 is a schematic sectional view showing an example of a semiconductor chip package of the present invention.

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

[Resin composition]
The resin composition of the present invention is a resin composition comprising (a) an elastomer, (b) an epoxy resin having an aromatic structure, (c) an inorganic filler, and (d) a dihydroxynaphthalene compound, ) When the content of the component is 100% by mass of the nonvolatile component of the resin composition excluding the (c) component, the content is 30% by mass to 85% by mass, and the content of the (c) component is the resin composition. When the non-volatile component is 100 mass%, it is 50 mass% to 95 mass%, and the elastic modulus at 23 ° C. of the thermoset obtained by thermosetting the resin composition at 180 ° C. for 1 hour is 18 GPa or less.

  From the viewpoint of improving the peel strength and heat resistance of the resin composition of the present invention and further suppressing the occurrence of warpage, the resin composition comprises (a) an elastomer, (b) an epoxy resin having an aromatic structure, (c ) An inorganic filler, and (d) a dihydroxynaphthalene compound. The resin composition may further contain (e) a curing agent, (f) a curing accelerator, and (g) a flame retardant as necessary. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Elastomer>
The resin composition includes (a) an elastomer. In the present invention, the elastomer means a resin having flexibility, and is not particularly limited. For example, in the molecule, a butadiene structural unit, a polysiloxane structural unit, a (meth) acrylate structural unit, an alkylene structural unit, an alkyleneoxy structural unit. , A resin exhibiting flexibility by having one or more structures selected from an isoprene structural unit, an isobutylene structural unit, and a polycarbonate structural unit. By including a flexible resin such as component (a), the plating peel strength against copper and the like can be improved, and the occurrence of warpage and the like can be further suppressed.

  More specifically, the component (a) includes butadiene structural units such as polybutadiene and hydrogenated polybutadiene, polysiloxane structural units such as silicone rubber, (meth) acrylate structural units, alkylene structural units (preferably having 2 to 2 carbon atoms). 15, more preferably 3 to 10 carbon atoms, more preferably 5 to 6 carbon atoms), an alkyleneoxy structural unit (preferably 2 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, still more preferably) It preferably has one or more structural units selected from 5 to 6 carbon atoms, isoprene structural units, isobutylene structural units, and polycarbonate structural units, and has a butadiene structural unit, polysiloxane structural unit, (meta ) Acrylate structural unit, isoprene structural unit, isobutylene structural unit, or Preferably it has one or more structural units selected from polycarbonate structural units, butadiene structural units, have one or more structural units selected from (meth) acrylate structural units is more preferable. “(Meth) acrylate” refers to methacrylate and acrylate.

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

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

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

  The component (a) is not particularly limited as long as it is a flexible resin, but preferably has a functional group capable of reacting with the component (b) described later. In addition, as a functional group which can react with (b) component, the functional group which appears by heating shall also be included.

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

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

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

  The functional group equivalent when the butadiene resin has a functional group is preferably 100 to 10,000, and more preferably 200 to 5000. The functional group equivalent is the number of grams of resin containing 1 gram equivalent of functional group. For example, the epoxy group equivalent can be measured according to JIS K7236. The hydroxyl equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

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

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

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

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

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

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

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

  The number average molecular weight (Mn) and functional group equivalent of the carbonate resin are the same as those of the butadiene resin, and the preferred ranges are also the same.

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

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

  Further, a suitable embodiment of the further component (a) contains a polysiloxane resin, an alkylene resin, an alkyleneoxy resin, for example, “YX-7180” (an alkylene structure having an ether bond) manufactured by Mitsubishi Chemical Corporation. Resin), isoprene resin, and isobutylene resin.

  Specific examples of the polysiloxane resin include “SMP-2006”, “SMP-2003 PGMEA”, and “SMP-5005 PGMEA” manufactured by Shin-Etsu Silicone Co., Ltd. Moreover, linear polyimide (WO2010 / 053185) etc. which use amine group terminal polysiloxane and a tetrabasic acid anhydride as a raw material are mentioned. Specific examples of the alkylene resin include “PTXG-1000” and “PTXG-1800” manufactured by Asahi Kasei Fibers Corporation. Specific examples of the isoprene resin include “KL-610” and “KL613” manufactured by Kuraray Co., Ltd. Specific examples of the isobutylene resin include “SIBSTAR-073T” (styrene-isobutylene-styrene triblock copolymer) and “SIBSTAR-042D” (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation. .

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

  The content of the component (a) in the resin composition is 30% by mass to 85% by mass when the nonvolatile component of the resin composition excluding the component (c) is 100% by mass from the viewpoint of imparting flexibility. Preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less. The lower limit is preferably 35% by mass or more, more preferably 45% by mass or more, and further preferably 55% by mass or more.

<(B) Epoxy resin having aromatic structure>
The resin composition includes (b) an epoxy resin having an aromatic structure. The epoxy resin having an aromatic structure (hereinafter also simply referred to as “epoxy resin”) is not particularly limited as long as it has an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles.

  Examples of the epoxy resin having an aromatic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, and naphthol. Novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin having aromatic structure, aromatic structure Having glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having aromatic structure, having aromatic structure Epoxy resin having tadiene structure, alicyclic epoxy resin having aromatic structure, heterocyclic epoxy resin, spiro ring-containing epoxy resin having aromatic structure, cyclohexanedimethanol type epoxy resin having aromatic structure, naphthylene ether Type epoxy resin, trimethylol type epoxy resin having an aromatic structure, tetraphenylethane type epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. The component (b) is more preferably at least one selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, and naphthalene type epoxy resin, and bisphenol F type epoxy resin and naphthalene. More preferably, it is a type epoxy resin.

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

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

  The liquid epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule and having a liquid aromatic ring structure at a temperature of 20 ° C., and the solid epoxy resin has three or more epoxy in one molecule. An epoxy resin having a group and having a solid aromatic ring structure at a temperature of 20 ° C. is preferred.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin having an aromatic structure, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene. Ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin, naphthy A renether type epoxy resin is more preferable, and a naphthalene type tetrafunctional epoxy resin and a naphthylene ether type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” manufactured by DIC Corporation. "(Cresol novolac type epoxy resin)", "N-695" (Cresol novolac type epoxy resin), "HP-7200", "HP-7200L", "HP-7200HH", "HP-7200H", "HP-7200HHH "(Dicyclopentadiene type epoxy resin)", "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type epoxy resin), Nippon Kayaku Co., Ltd. “EPPN-502H” (trisphenol type epoxy resin), “ C7000L "(naphthol novolac type epoxy resin)," NC3000H "," NC3000 "," NC3000L "," NC3100 "(biphenyl type epoxy resin)," ESN475V "(naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. “ESN485” (naphthol novolak type epoxy resin), “YX4000H”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YL7760” (bisphenol AF type) manufactured by Mitsubishi Chemical Corporation Epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation , Mitsubishi Chemical Corporation “JER1010” (solid bisphenol A type epoxy resin), “jER1031S” (tetraphenylethane type epoxy resin), “157S70” (bisphenol novolak type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YX4000HK” (Bi Xylenol type epoxy resin), “YX8800” (anthracene type epoxy resin), “PG-100”, “CG-500” manufactured by Osaka Gas Chemical Co., Ltd., “YL7800” (fluorene type epoxy manufactured by Mitsubishi Chemical Corporation) Resin), “jER1031S” (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used alone or in combination of two or more.

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

  The content of the epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. That's it. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.

  In addition, in this invention, content of each component in a resin composition is a value when the non-volatile component in a resin composition is 100 mass% unless there is separate description.

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

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

<(C) Inorganic filler>
The resin composition includes (c) an inorganic filler. The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle size of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, and even more preferably 2.2 μm or less, from the viewpoint of improving the circuit embedding property and obtaining an insulating layer having a low surface roughness. Preferably it is 2 micrometers or less. Although the minimum of this average particle diameter is not specifically limited, Preferably it is 0.01 micrometer or more, More preferably, it is 0.05 micrometer or more, More preferably, it is 0.1 micrometer or more. Examples of commercially available inorganic fillers having such an average particle size include, for example, “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C” manufactured by Admatechs, manufactured by Denki Kagaku Kogyo Co., Ltd. “UFP-30”, “Silfil NSS-3N”, “Silfil NSS-4N”, “Silfil NSS-5N” manufactured by Tokuyama Corporation, “SC2500SQ”, “SO-C6”, “SO-C6” manufactured by Admatechs Co., Ltd. -C4 "," SO-C2 "," SO-C1 "and the like.

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

  Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents from the viewpoint of improving moisture resistance and dispersibility. It is preferable that it is processed with 1 or more types of surface treating agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (hexamethyldisilazane) manufactured by KK, "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type) Silane coupling agent).

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is more preferable from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the sheet form. preferable.

  The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by Horiba, Ltd. can be used.

  The content of the inorganic filler in the resin composition is 50% by mass to 95% by mass from the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion. Preferably it is 55 mass% or more, More preferably, it is 60 mass% or more, More preferably, it is 65 mass% or more. The upper limit is preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less from the viewpoint of mechanical strength of the insulating layer, particularly elongation.

<(D) Dihydroxynaphthalene compound>
The resin composition contains (d) a dihydroxynaphthalene compound. By including (d) component, generation | occurrence | production of curvature is suppressed and it becomes possible to provide the resin composition which is excellent in peel strength and heat resistance. The two hydroxy groups of component (d) react with component (b) during thermosetting, and the bond between component (b) and component (d) becomes stronger, improving peel strength and heat resistance. To do. In addition, since the component (d) does not react with the component (b) and volatilize at the time of thermosetting, warpage that occurs due to volatilization is suppressed.

（式（１）中、Ｒ^１は、置換基を有していてもよい炭素原子数１〜６のアルキル基、置換基を有していてもよい炭素原子数１〜６のアルコキシ基、又は置換基を有していてもよい炭素原子数６〜１０のアリール基を表し、ｎは０〜４の整数を表す。Ｒ^１が複数存在する場合、それぞれのＲ^１は同一であってもよく、互いに異なっていてもよい。Ｒ^２は、単結合又は置換基を有していてもよい２価の連結基を表し、ｍは１〜６の整数を表す。Ｒ^２が複数存在する場合、それぞれのＲ^２は同一であってもよく、互いに異なっていてもよい。） The component (d) is not particularly limited as long as it is a naphthalene compound having two hydroxy groups, and a commercially available product may be used. Especially, it is preferable that (d) component is a dihydroxy naphthalene compound represented by following formula (1).

(In Formula (1), R ¹ is an alkyl group having 1 to 6 carbon atoms which may have a substituent, an alkoxy group having 1 to 6 carbon atoms which may have a substituent, or Represents an optionally substituted aryl group having 6 to 10 carbon atoms, and n represents an integer of 0 to 4. When a plurality of R ¹ are present, each R ¹ may be the same. R ² represents a single bond or a divalent linking group which may have a substituent, m represents an integer of 1 to 6. When a plurality of R ² are present, Each R ² may be the same or different from each other.

R ¹ has an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkoxy group having 1 to 6 carbon atoms, or a substituent. Or an aryl group having 6 to 10 carbon atoms. The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably an alkyl group having 1 to 3 carbon atoms. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, etc. Is mentioned.

  The alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and further preferably an alkoxy group having 1 to 3 carbon atoms. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy Groups and the like. The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be linear, branched or cyclic, but are preferably linear or branched alkyl groups and alkoxy groups.

  Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.

In the formula (1), two OH groups, —H, —R ² —, and n R ^{1 s} may be bonded to any one of the 1-position to the 8-position of the naphthalene ring.

The alkyl group having 1 to 6 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, or the aryl group having 6 to 10 carbon atoms which R ¹ represents may have a substituent.

The substituent is not particularly limited, for example, a halogen atom, -OH, _{-O-C 1-6} alkyl group, -N _{(C 1-6 alkyl) 2, C 1-6 alkyl, C 6- A 10} aryl group, —NH ₂ , —CN, —C (O) O—C _1-6 alkyl group, —COOH, —C (O) H, —NO _{2 and the} like.

Here, the term “C _pq ” (p and q are positive integers, satisfying p <q) means that the number of carbon atoms of the organic group described immediately after this term is p to q. Represents something. For example, the expression “C _1-6 alkyl group” refers to an alkyl group having 1 to 6 carbon atoms.

  The above-described substituent may further have a substituent (hereinafter sometimes referred to as “secondary substituent”). As the secondary substituent, the same substituents as described above may be used unless otherwise specified.

  n represents an integer of 0 to 4, preferably represents an integer of 0 to 3, more preferably represents an integer of 0 to 2, and 0 is even more preferable.

R ² represents a single bond or a divalent linking group which may have a substituent. The divalent linking group includes an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -C (= O)-, -C (= O) -O-, an oxygen atom, a sulfur atom, and C (= O) NR -, -NR- (R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms), and a group formed by a combination thereof.

As the alkylene group, an alkylene group having 1 to 6 carbon atoms is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is particularly preferable. The number of carbon atoms of the substituent is not included in the number of carbon atoms. The alkylene group represented by R ² may be linear, branched or cyclic, but is preferably a linear alkylene group. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

The alkenylene group is preferably an alkenylene group having 2 to 6 carbon atoms, more preferably an alkenylene group having 2 to 5 carbon atoms, and particularly preferably an alkenylene group having 2 to 4 carbon atoms. The number of carbon atoms of the substituent is not included in the number of carbon atoms. The alkenylene group represented by R ² may be linear, branched or cyclic, but is preferably a linear alkenylene group. Examples of such alkenylene group include ethylenylene group, propynylene group, butenylene group, pentenylene group, hexenylene group and the like.

The alkynylene group is preferably an alkynylene group having 2 to 6 carbon atoms, more preferably an alkynylene group having 2 to 5 carbon atoms, and particularly preferably an alkynylene group having 2 to 4 carbon atoms. The number of carbon atoms of the substituent is not included in the number of carbon atoms. The alkynylene group represented by R ² may be linear, branched or cyclic, but is preferably a linear alkynylene group. Examples of such an alkynylene group include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, and the like.

  As the arylene group, an arylene group having 6 to 10 carbon atoms is preferable. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Examples of the arylene group include a phenylene group and a naphthylene group.

Among these, R ² is preferably a single bond or a group consisting of a combination of an alkylene group and an arylene group, more preferably a group consisting of a single bond or a combination of a methylene group and a phenylene group.

The divalent linking group represented by R ² may have a substituent. The substituent has the same meaning as the substituent that the alkyl group have 1 to 6 carbon atoms represented by R ^1, and preferred ranges are also the same.

  m represents an integer of 1 to 6, preferably represents an integer of 1 to 5, more preferably represents an integer of 1 to 3, and further preferably represents 1.

（式（２）中、Ｒ^１１は、置換基を有していてもよい炭素原子数１〜６のアルキル基、置換基を有していてもよい炭素原子数１〜６のアルコキシ基、又は置換基を有していてもよい炭素原子数６〜１０のアリール基を表し、ｎ１は０〜６の整数を表す。Ｒ^１１が複数存在する場合、それぞれのＲ^１１は同一であってもよく、互いに異なっていてもよい。） The component (d) is preferably a dihydroxynaphthalene compound represented by the following formula (2).

(In Formula (2), R ¹¹ is an alkyl group having 1 to 6 carbon atoms which may have a substituent, an alkoxy group having 1 to 6 carbon atoms which may have a substituent, or Represents an aryl group having 6 to 10 carbon atoms which may have a substituent, and n1 represents an integer of 0 to 6. When a plurality of R ¹¹ are present, each R ¹¹ may be the same. May be different from each other.)

R ¹¹ has the same meaning as R ¹ in formula (1), and the preferred range is also the same. n1 represents an integer of 0 to 6, preferably represents an integer of 0 to 4, more preferably represents an integer of 0 to 3, and represents an integer of 0 to 2, 0 or 1, or 0. Further preferred.

In the formula (2), two OH groups and n1 R ¹¹ may be bonded to any of the 1-position to the 8-position of the naphthalene ring.

式中、ｍ１は０から６の整数を表す。 Specific examples of the component (d) include 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and dihydroxys shown below. And naphthalene compounds. The present invention is not limited to these.

In the formula, m1 represents an integer of 0 to 6.

  (D) Content of a component becomes like this. Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less, or 0.5 mass% or less. The lower limit is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more.

<(E) Curing agent>
The resin composition may contain (e) a curing agent. The curing agent is not particularly limited as long as it has a function of curing the resin such as component (b). For example, phenolic curing agent, naphthol curing agent, active ester curing agent, benzoxazine curing agent, cyanate ester Examples thereof include a system curing agent and a carbodiimide curing agent. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together. The component (e) is preferably at least one selected from a phenolic curing agent, a naphthol curing agent, an active ester curing agent, and a cyanate ester curing agent.

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

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

  From the viewpoint of obtaining an insulating layer having excellent adhesion to the wiring layer, an active ester curing agent is also preferable. Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolac, and an active ester compound containing a benzoylated product of a phenol novolac are preferred, Of these, active ester compounds having a naphthalene structure and active ester compounds having a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

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

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

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolac polyfunctional cyanate ester resins), “BA230”, “BA230S75” (bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. For example, a prepolymer partially or wholly converted into a trimer).

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

  Although content of the hardening | curing agent in a resin composition is not specifically limited, Preferably it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less. The lower limit is not particularly limited but is preferably 1% by mass or more.

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

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

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

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

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

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

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

  Although content of the hardening accelerator in a resin composition is not specifically limited, 0.01 mass%-3 mass% are preferable when the non-volatile component total amount of (b) component and a hardening | curing agent is 100 mass%.

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

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

  When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and still more preferably. 0.5 mass%-10 mass% are further more preferable.

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

  From the viewpoint of suppressing warpage, the resin composition of the present invention has an elastic modulus at 23 ° C. of 18 ° C. or less, preferably 15 GPa or less, and 13 GPa or less. It is more preferably 11 GPa or less, 10 GPa or less, 9 GPa or less, or 8 GPa or less. Although it does not specifically limit about a minimum, For example, it can be set as 0.01 GPa or more, 0.5 GPa or more, 1 GPa or more, etc. The elastic modulus can be measured according to the method described in <Elastic modulus of resin composition> described later.

  The resin composition (or resin composition layer) of the present invention exhibits the characteristic that the occurrence of warpage is suppressed. The magnitude of the warp is preferably less than 3 cm, more preferably 1.5 cm or less. The warpage can be measured according to the method described in <Evaluation of warpage> described later.

  A cured product of the resin composition (or resin composition layer) of the present invention (for example, a cured product obtained by curing at 180 ° C. for 90 minutes) exhibits good peel strength. That is, an insulating layer exhibiting good peel strength is provided. The peel strength of the cured product of the resin composition (or resin composition layer) is preferably 1.5 kgf / cm or less, more preferably 1 kgf / cm or less, and even more preferably 0.7 kgf / cm or less. The upper limit may be 0.1 kgf / cm or more. The measuring method of peel strength can be measured according to the method described in <Evaluation of peel strength> described later.

  The elastic modulus of the resin composition layer obtained by thermosetting the resin composition (or resin composition layer) of the present invention at 180 ° C. for 90 minutes and the resin composition (or resin composition layer) obtained by thermosetting at 210 ° C. for 90 minutes. ) Is preferably less than 2 GPa, more preferably 1.5 GPa or less, and even more preferably 1 GPa or less. The lower limit is preferably 0 GPa or more. Therefore, a cured product obtained by thermally curing the resin composition (or resin composition layer) of the present invention (for example, a cured product obtained by curing at 180 ° C. for 90 minutes or 210 ° C. for 90 minutes) is good. Shows heat resistance. That is, an insulating layer exhibiting good heat resistance is provided. The heat resistance can be measured according to the method described in <Evaluation of heat resistance> in Examples described later.

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

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

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

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

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. , “AL-5”, “AL-7”, “Lumirror T6AM” manufactured by Toray Industries, Inc., and the like.

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

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

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

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

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

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

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of thinning, the thickness of the sheet-like fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and even more preferably 600 μm or less. In particular, in the present invention, since the plating depth can be suppressed small, it is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less. Although the minimum of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it may be 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more, etc.

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

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

  The resin sheet of the present invention can be suitably used for forming an insulating layer of a circuit board in the production of a semiconductor chip package. The resin sheet of the present invention is also suitable for forming a wide range of other applications requiring high insulation reliability, for example, an insulating layer of a circuit board such as a printed wiring board on which a semiconductor chip package is mounted. Can be used. Among them, the resin sheet of the present invention includes the resin composition of the present invention, and the resin composition of the present invention suppresses warpage, so that it is applied to wiring methods such as WLP (Wafer Level Package) and MUF (Molding Under Filling). It can be preferably used. Therefore, in one embodiment, the resin sheet of the present invention can be used for an insulating layer of a circuit board.

[Semiconductor chip package]
The semiconductor chip package of the present invention has a semiconductor chip mounted on a circuit board, and the surface of the circuit board on which the semiconductor chip is mounted includes an insulating layer formed of a cured product of the resin composition of the present invention. .

  The semiconductor package of the present invention can be suitably used for a WLP wiring method. As shown in FIG. 1, the WLP wiring method includes a circuit board 14 and a semiconductor chip 15. The circuit board 14 includes a substrate 11, a wiring layer 12 provided on the substrate 11, and an insulating layer 13 provided on the surface of the wiring layer 12 opposite to the surface on the substrate 11 side.

For example, the semiconductor chip package of the present invention can be manufactured by a method including the following steps (I) to (II) using the above-described resin sheet.
(I) The process of preparing the circuit board containing the insulating layer which consists of hardened | cured material of a resin composition (II) The process of joining a semiconductor chip on a circuit board

<Process (I)>
In step (I), a circuit board including an insulating layer made of a cured product of the resin composition is prepared. The circuit board is not particularly limited as long as it has circuit wiring and the insulating layer includes an insulating layer made of a cured product of the resin composition of the present invention. When the circuit board includes a plurality of insulating layers, at least one insulating layer may be an insulating layer made of a cured product of the resin composition of the present invention.

  The use of a circuit board having circuit wiring in which the ratio (L / S) of the circuit width (line; L) of the circuit board to the width (space; S) between the circuits is 20 μm / 20 μm or less (that is, wiring pitch is 40 μm or less). Is possible. Furthermore, it is possible to use a circuit board having circuit wiring of L / S = 15 μm / 15 μm or less (wiring pitch 30 μm or less) and L / S = 10 μm / 10 μm or less (wiring pitch 20 μm or less). Note that the wiring pitch of the circuit wiring does not have to be the same over the entire circuit board. The wiring pitch refers to the total distance of lines and spaces.

Although the manufacturing method of a circuit board is not specifically limited, For example, it can manufacture by the method including the process of following (1)-(3).
(1) Step of forming a wiring layer on a substrate (2) Step of laminating a resin sheet on the wiring layer so that the resin composition layer of the resin sheet is bonded to the wiring layer (3) Resin composition layer Process of thermosetting the insulation layer

  Examples of the substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate, and the substrate has a metal layer such as a copper foil formed on the surface. It may be.

  The wiring layer can be formed by a plating method using a dry film having a desired pattern as a plating mask.

  The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, and for example, a dry film such as a novolak resin or an acrylic resin can be used. A commercial item may be used for a dry film, for example, "ALPHO 20A263" by Nikko Materials Co., Ltd. which is a dry film with a PET film can be used. The dry film may be laminated on one side of the support substrate, or may be laminated on both sides of the support substrate.

  The lamination conditions of the substrate and the dry film are the same as the lamination conditions in step (2) described later, and the preferred range is also the same.

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

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

  The thickness of the wiring layer is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 7 to 20 μm, or 15 μm, although it depends on the desired semiconductor chip package design.

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

  After forming the wiring layer, the surface of the wiring can be roughened as necessary. As the surface roughening agent, for example, “CZ-8000 series” manufactured by MEC Co., Ltd. can be used. A resin sheet is laminated on the wiring layer so that the resin composition layer of the resin sheet is bonded to the wiring layer. The resin sheet is preferably laminated on the substrate so that the wiring layer is embedded in the resin composition layer.

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

  Lamination of the resin sheets may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 13 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Nikko Materials, a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and the like.

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

  The support may be removed before the resin sheets are laminated or may be removed after the lamination.

  After laminating the resin composition layer, the resin composition layer is thermoset to form an insulating layer. The thermosetting conditions for the resin composition layer are not particularly limited, and the conditions normally employed when forming the insulating layer of the circuit board may be used.

  For example, although the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably in the range of 170 ° C to 200 ° C.) and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

  Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is formed at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  In another embodiment, in the present invention, it can be manufactured using a prepreg instead of the resin sheet described above. The manufacturing method is basically the same as when using a resin sheet.

  After forming the insulating layer, the insulating layer is polished or ground to expose the wiring layer. Alternatively, a hole may be formed in the insulating layer to form a via hole in the insulating layer to expose the wiring layer.

<Process (II)>
After step (I), in step (II), the semiconductor chip is bonded to the circuit board.

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

  In a preferred embodiment, the semiconductor chip is pressure-bonded to the circuit board. As the crimping conditions, for example, the crimping temperature is in the range of 120 ° C. to 240 ° C. (preferably in the range of 130 ° C. to 200 ° C., more preferably in the range of 140 ° C. to 180 ° C.), and the crimping time is in the range of 1 second to 60 seconds. (Preferably 5 to 30 seconds).

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

  After the semiconductor chip is bonded to the circuit board, the semiconductor chip package is obtained by filling the semiconductor chip with a mold underfill material by, for example, the MUF (Molding Under Filling) method. The method of filling with the mold underfill material can be performed by a known method.

[Semiconductor device]
Semiconductor devices to be mounted with the semiconductor chip package of the present invention include electrical products (for example, computers, mobile phones, smartphones, tablet PCs, digital cameras and televisions) and vehicles (for example, motorcycles, automobiles, trains, And various semiconductor devices used for ships and aircraft).

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

<Manufacture of elastomer A>
In a reaction vessel, 50 g of G-3000 (bifunctional hydroxy group-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxy group equivalent = 1798 g / eq., Solid content: 100 mass%: Nippon Soda Co., Ltd.) 23.5 g of ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. When the temperature became uniform, the temperature was raised to 50 ° C., and while further stirring, 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) Was added and the reaction was carried out for about 3 hours. The reaction was then cooled to room temperature before 8.96 g benzophenonetetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g triethylenediamine, and ethyl diglycol. 40.4 g of acetate (manufactured by Daicel Corporation) was added, the temperature was raised to 130 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. The confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a 100 μm mesh filter cloth to obtain an elastomer A having a butadiene structure and an acid anhydride group.
Viscosity: 7.5 Pa · s (25 ° C, E-type viscometer)
Acid value: 16.9 mgKOH / g
Solid content: 50% by mass
Number average molecular weight: 13723
Glass transition temperature: -10 ° C
Content of polybutadiene structure part: 50 / (50 + 4.8 + 8.96) × 100 = 78.4% by mass.
Functional group equivalent: 45943 g / eq

<Manufacture of elastomer B>
Polyethylene diol (number average molecular weight: about 1000, hydroxyl group equivalent: 500, nonvolatile content: 100%, “C-1015N” manufactured by Kuraray Co., Ltd.) 80 g and dibutyltin dilaurate 0.01 g in diethylene glycol monoethyl ether The mixture was uniformly dissolved in 37.6 g of acetate (“Ethyl Diglycol Acetate” manufactured by Daicel Corporation) to obtain a mixture, and the mixture was heated to 50 ° C. and further stirred with toluene-2,4- 27.8 g of diisocyanate (isocyanate group equivalent: 87.08) was added, and the reaction was carried out for about 3 hours, after which the reaction was cooled to room temperature and then benzophenone tetracarboxylic dianhydride (acid anhydride equivalent). : 161.1) 14.3 g, triethylenediamine 0.12 g, and diethylene glycol Was added Roh ethyl ether acetate (KK Daicel "Ethyl diglycol acetate") 84.0 g, stirring the temperature was raised to 130 ℃, .FT-IR than the 2250 cm ^-1 which was about 4 hours After confirming the disappearance of the NCO peak, the reaction was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a filter cloth having an opening of 100 μm to obtain a carbonate structure and an acid anhydride. An elastomer B having groups was obtained.
Viscosity: 3 Pa · s (25 ° C, E-type viscometer)
Solid content: 50% by mass
Number average molecular weight: 8500
Glass transition temperature: 3 ° C
Functional group equivalent: 15241 g / eq

[Production Example 1: Production of resin varnish 1]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, Mitsubishi Chemical Corporation "JER806" 3 parts, naphthalene type epoxy resin (epoxy equivalent 151, DIC Corporation "HP4032") 3 parts, imidazole derivative (2 -Phenyl-4-methylimidazole, Shikoku Kasei Co., Ltd., “2P4MZ”) 0.05 part, 1,4-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.) 0.15 part, Elastomer A 30 parts, Phenyl 90 parts of spherical silica (manufactured by Admatechs, “SO-C6”, average particle diameter 2 μm) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), cresol novolac resin (DIC Corporation "KA-1163", phenolic hydroxyl group equivalent: 118 g / eq) 4 parts, methyl ethyl ketone The emissions 15 parts were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 1.

[Production Example 2: Production of resin varnish 2]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, Mitsubishi Chemical Corporation "JER806" 3 parts, naphthalene type epoxy resin (epoxy equivalent 151, DIC Corporation "HP4032") 3 parts, imidazole derivative (2 -Phenyl-4-methylimidazole, Shikoku Kasei Co., Ltd., "2P4MZ") 0.05 part, 1,6-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.) 0.15 part, Elastomer A 30 parts, Phenyl 95 parts of spherical silica (manufactured by Admatechs, “SO-C6”, average particle size 2 μm) surface-treated with an aminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”), cresol novolac resin (DIC Corporation, “KA-1163”, phenolic hydroxyl group equivalent: 118 g / eq), 4 parts, methyl ethyl ketone 15 parts of Ton were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish 2.

[Production Example 3: Production of resin varnish 3]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, Mitsubishi Chemical Corporation "JER806" 3 parts, naphthalene type epoxy resin (epoxy equivalent 151, DIC Corporation "HP4032") 3 parts, imidazole derivative (2 -Phenyl-4-methylimidazole, Shikoku Kasei Co., Ltd., "2P4MZ") 0.05 part, 1,4-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.) 0.15 part, epoxy group-containing acrylic ester Copolymer resin (manufactured by Nagase ChemteX Corp., “Taisan Resin SG-80H”, solid content 20%, MEK / toluene solution, Tg 11 ° C., functional group equivalent 145,000 g / eq, weight average molecular weight Mw 350,000), Spheres surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts of silica (manufactured by Admatechs, “SO-C6”, average particle size 2 μm), 4 parts of cresol novolac resin (“KA-1163”, manufactured by DIC Corporation, phenolic hydroxyl group equivalent: 118 g / eq), 15 parts of methyl ethyl ketone was mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin varnish 3.

[Production Example 4: Production of resin varnish 4]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, Mitsubishi Chemical Corporation "JER806" 3 parts, naphthalene type epoxy resin (epoxy equivalent 151, DIC Corporation "HP4032") 3 parts, imidazole derivative (2 -Phenyl-4-methylimidazole, Shikoku Kasei Co., Ltd., "2P4MZ") 0.05 part, 1,5-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.) 0.15 part, acrylate copolymer resin (Manufactured by Nagase ChemteX Corporation, “Taisan Resin SG-80H”, solid content 20%, MEK / toluene solution, Tg 11 ° C., functional group equivalent 14285 g / eq, weight average molecular weight Mw 350,000) 75 parts, phenylaminosilane Spherical silica surface treated with a coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 100 parts by Admatechs, "SO-C6", average particle size 2 µm), 4 parts by cresol novolac resin ("KA-1163" by DIC, phenolic hydroxyl equivalent: 118 g / eq), 15 parts by methyl ethyl ketone Then, the resin varnish 4 was produced by uniformly dispersing with a high-speed rotating mixer.

[Production Example 5: Production of resin varnish 5]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, Mitsubishi Chemical Corporation "JER806" 3 parts, naphthalene type epoxy resin (epoxy equivalent 151, DIC Corporation "HP4032") 3 parts, imidazole derivative (2 -Phenyl-4-methylimidazole, Shikoku Kasei Co., Ltd., "2P4MZ") 0.05 part, 1,4-dihydroxynaphthalene (Tokyo Kasei Kogyo Co., Ltd.) 0.15 part, elastomer B 30 parts, phenylaminosilane 100 parts of spherical silica (manufactured by Admatechs Co., Ltd., “SO-C6”, average particle size 2 μm) surface-treated with a coupling agent (Shin-Etsu Chemical Co., Ltd., “KBM573”), cresol novolac resin ( "KA-1163" manufactured by DIC Corporation, 4 parts of phenolic hydroxyl group equivalent: 118 g / eq), methyl ethyl ketone The emissions 15 parts were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 5.

[Production Example 6: Production of resin varnish 6]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, Mitsubishi Chemical Corporation "JER806" 3 parts, naphthalene type epoxy resin (epoxy equivalent 151, DIC Corporation "HP4032") 3 parts, imidazole derivative (2 Surface treatment with 0.05 parts of phenyl-4-methylimidazole, “2P4MZ” manufactured by Shikoku Kasei Co., Ltd., 30 parts of elastomer A, and a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) 90 parts of spherical silica (manufactured by Admatechs Co., Ltd., “SO-C6”, average particle size 2 μm), cresol novolac resin (“KA-1163” produced by DIC Corporation, phenolic hydroxyl group equivalent: 118 g / eq) 4 parts and 15 parts of methyl ethyl ketone are mixed and dispersed uniformly with a high-speed rotary mixer. It was produced.

[Production Example 7: Production of resin varnish 7]
Bisphenol F type epoxy resin (epoxy equivalent 160-170, Mitsubishi Chemical Corporation "JER806" 3 parts, naphthalene type epoxy resin (epoxy equivalent 151, DIC Corporation "HP4032") 3 parts, imidazole derivative (2 -Phenyl-4-methylimidazole, 0.05 part of Shikoku Kasei Co., Ltd., “2P4MZ”, acrylic ester copolymer resin (manufactured by Nagase ChemteX Corp., “Taisan Resin SG-80H”, solid content 20 % MEK / toluene solution) 75 parts, spherical silica surface-treated with a phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”) (manufactured by Admatechs, “SO-C6”, average) 100 parts of particle size 2 μm), cresol novolac resin (“KA-1163” manufactured by DIC Corporation), phenolic water Group equivalent: 118g / eq) 4 parts of a mixture of 15 parts of methyl ethyl ketone, and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 7.

<Elastic modulus of resin composition>
The untreated surface of the release PET film (Lintec Co., Ltd. “501010”, thickness 38 μm, 240 mm square) is a glass cloth base epoxy resin double-sided copper-clad laminate (Matsushita Electric Works “R5715ES”, thickness) 0.7 mm, 250 mm square) was placed on a glass cloth base epoxy resin double-sided copper-clad laminate, and the four sides of the release film were fixed with polyimide adhesive tape (width 10 mm).

  Each resin sheet (230 mm square) produced in Examples and Comparative Examples was released from a resin composition layer using a batch-type vacuum pressurization laminator (Nikko Materials Co., Ltd. 2-stage buildup laminator CVP700). Lamination was performed at the center so as to contact the release surface of the PET film. The laminating process was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

  Subsequently, the support was peeled off, and the resin composition layer was thermally cured under curing conditions at 180 ° C. for 60 minutes.

  After thermosetting, the polyimide adhesive tape was peeled off, and the resin composition layer was removed from the glass cloth base epoxy resin double-sided copper-clad laminate. Further, the release PET film was peeled from the resin composition layer to obtain a sheet-like cured product. The sheet-like cured product is referred to as an evaluation cured product. The obtained cured product for evaluation was cut into a dumbbell shape No. 1 to obtain a test piece. The test piece was subjected to tensile strength measurement using a tensile tester “RTC-1250A” manufactured by Orientec Co., and the elastic modulus at 23 ° C. was obtained. The measurement was performed according to JIS K7127. This operation was performed 5 times, and the average value of the top 3 points was shown in the table.

[Example 1: Production of resin sheet 1]
On a polyethylene terephthalate film (thickness 75 μm, hereinafter abbreviated as “PET film”), the resin varnish 1 is applied with a die coater so that the thickness of the resin composition layer after drying is 60 μm. The resin sheet 1 was obtained by drying at 10 ° C. (average 100 ° C.) for 10 minutes.

[Example 2: Production of resin sheet 2]
In Example 1, the resin varnish 1 was changed to the resin varnish 2. Except for the above, a resin sheet 2 was obtained in the same manner as in Example 1.

[Example 3: Production of resin sheet 3]
In Example 1, the resin varnish 1 was changed to the resin varnish 3. Except for the above, a resin sheet 3 was obtained in the same manner as in Example 1.

[Example 4: Production of resin sheet 4]
In Example 1, the resin varnish 1 was changed to the resin varnish 4. Except for the above, a resin sheet 4 was obtained in the same manner as in Example 1.

[Example 5: Production of resin sheet 5]
In Example 1, the resin varnish 1 was changed to the resin varnish 5. Except for the above, a resin sheet 5 was obtained in the same manner as in Example 1.

[Comparative Example 1: Production of resin sheet 6]
In Example 1, the resin varnish 1 was changed to the resin varnish 6. Except for the above, a resin sheet 6 was obtained in the same manner as in Example 1.

[Comparative Example 2: Production of resin sheet 7]
In Example 1, the resin varnish 1 was changed to the resin varnish 7. Except for the above, a resin sheet 7 was obtained in the same manner as in Example 1.

[Evaluation]
<Evaluation of warpage>
The resin sheets prepared in Examples and Comparative Examples were placed on the entire surface of a copper foil (“JTC foil” manufactured by JX Nippon Mining & Metals Co., Ltd., copper foil thickness 18 μm, size 15 cm × 18 cm), and batch-type vacuum processing was performed. After laminating with a pressure laminator (Nikko Materials Co., Ltd. 2-stage buildup laminator “CVP700”), the PET film was peeled off, and the resin sheet was thermally cured in an oven at 180 ° C. for 90 minutes to obtain an evaluation sample. Of the four sides of the obtained copper foil with a resin sheet, three sides are fixed to the SUS plate with polyimide tape, and the warp value is obtained by obtaining the height of the highest point from the SUS plate, and the warp size is 0 cm. More than 1.5 cm and less than 1.5 cm were evaluated as “◯”, 1.5 cm and less than 3 cm were evaluated as “Δ”, and 3 cm and more were evaluated as “×”.

<Evaluation of peel strength>
After laminating the resin sheets prepared in Examples and Comparative Examples to copper foil (“JTC foil” manufactured by JX Nippon Mining & Metals Co., Ltd., copper foil thickness 18 μm), the PET film was removed. The obtained copper foil with resin is made of glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, R5715ES manufactured by Matsushita Electric Works Co., Ltd.) 1 μm, etched with a chemical treatment agent (CZ8100), and then roughened on the copper surface) with a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd. 2-stage buildup laminator “CVP700”) did. Thereafter, thermosetting was performed at 180 ° C. for 90 minutes to prepare a sample. Cut the 10mm width and 100mm length into the prepared sample, peel off one end of the copper foil, and use a gripping tool (manufactured by TS KK, Autocom type testing machine, AC-50C-SL) The load (kgf / cm) when gripping and peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature (25 ° C.) was measured.

<Evaluation of heat resistance>
(Elastic modulus after curing at 180 ° C for 90 minutes)
After laminating the resin sheets prepared in Examples and Comparative Examples to copper foil (manufactured by JX Nippon Mining & Metals, “JTC foil”, copper foil thickness 18 μm), the PET film was removed. The obtained resin-coated copper foil was heat-treated in a hot air oven at 180 ° C. for 90 minutes to thermally cure the resin sheet to obtain a cured film. The copper foil on which the cured film was formed was immersed in a ferric chloride solution and removed by etching, and then dried at 100 ° C. for 10 minutes to produce a cured film alone from which the copper foil was removed. The cured film from which the copper foil was removed was subjected to a tensile test using a Tensilon universal testing machine (manufactured by A & D Co., Ltd.) in accordance with Japanese Industrial Standard (JIS K7127), and the elastic modulus was measured.

(Elastic modulus after curing at 210 ° C for 90 minutes)
After laminating the resin sheets prepared in Examples and Comparative Examples to copper foil (“JTC foil” manufactured by JX Nippon Mining & Metals Co., Ltd., copper foil thickness: 18 μm), the PET film was removed. The obtained resin-coated copper foil was heat-treated in a hot air oven at 210 ° C. for 90 minutes to thermally cure the resin sheet to obtain a cured film. The copper foil on which the cured film was formed was immersed in a ferric chloride solution and removed by etching, and then dried at 100 ° C. for 10 minutes to produce a cured film alone from which the copper foil was removed. The cured film from which the copper foil was removed was subjected to a tensile test using a Tensilon universal testing machine (manufactured by A & D Co., Ltd.) in accordance with Japanese Industrial Standard (JIS K7127), and the elastic modulus was measured.

  The difference between the elastic modulus after curing at 180 ° C. for 90 minutes and the elastic modulus after curing at 210 ° C. for 90 minutes was defined as “◯”, and “X” when 2 Gpa or more.

DESCRIPTION OF SYMBOLS 1 Semiconductor chip package 11 Board | substrate 12 Wiring layer 13 Insulating layer 14 Circuit board 15 Semiconductor chip

Claims (11)

A resin composition comprising (a) an elastomer, (b) an epoxy resin having an aromatic structure, (c) an inorganic filler, and (d) a dihydroxynaphthalene compound,
When the nonvolatile component of the resin composition excluding the component (c) is 100% by mass, the content of the component (a) is 30% by mass to 85% by mass,
(C) When content of a component makes the non-volatile component of a resin composition 100 mass%, it is 50 mass%-95 mass%,
The resin composition whose elastic modulus in 23 degreeC of the thermosetting material which heat-cured the resin composition at 180 degreeC for 1 hour is 18 GPa or less. The resin composition according to claim 1, wherein the component (d) is represented by the following formula (1).

(In Formula (1), R ¹ is an alkyl group having 1 to 6 carbon atoms which may have a substituent, an alkoxy group having 1 to 6 carbon atoms which may have a substituent, or Represents an optionally substituted aryl group having 6 to 10 carbon atoms, and n represents an integer of 0 to 4. When a plurality of R ¹ are present, each R ¹ may be the same. R ² represents a single bond or a divalent linking group which may have a substituent, m represents an integer of 1 to 6. When a plurality of R ² are present, Each R ² may be the same or different from each other. The resin composition according to claim 1 or 2, wherein the component (d) is represented by the following formula (2).

(In Formula (2), R ¹¹ is an alkyl group having 1 to 6 carbon atoms which may have a substituent, an alkoxy group having 1 to 6 carbon atoms which may have a substituent, or Represents an aryl group having 6 to 10 carbon atoms which may have a substituent, and n1 represents an integer of 0 to 6. When a plurality of R ¹¹ are present, each R ¹¹ may be the same. May be different from each other.)   The component (a) is one or more selected from butadiene structural units, polysiloxane structural units, (meth) acrylate structural units, alkylene structural units, alkyleneoxy structural units, isoprene structural units, isobutylene structural units, and polycarbonate structural units. The resin composition of any one of Claims 1-3 which has a structural unit.   The resin composition according to any one of claims 1 to 4, wherein the component (a) is at least one selected from a resin having a glass transition temperature of 25 ° C or lower and a resin that is liquid at 25 ° C. .   The resin composition according to claim 1, wherein the component (a) has a functional group capable of reacting with the component (b).   The resin composition according to any one of claims 1 to 6, wherein the component (a) has an imide structure.   The resin composition according to any one of claims 1 to 7, wherein the component (a) has a phenolic hydroxyl group.   The resin sheet which has a support body and the resin composition layer provided on this support body containing the resin composition of any one of Claims 1-8.   The circuit board in which the surface in which a semiconductor chip is mounted contains the insulating layer formed with the hardened | cured material of the resin composition of any one of Claims 1-8.   A semiconductor chip package in which a semiconductor chip is mounted on the circuit board according to claim 10.

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