TWI811399B - resin composition - Google Patents

resin composition Download PDF

Info

Publication number
TWI811399B
TWI811399B TW108125420A TW108125420A TWI811399B TW I811399 B TWI811399 B TW I811399B TW 108125420 A TW108125420 A TW 108125420A TW 108125420 A TW108125420 A TW 108125420A TW I811399 B TWI811399 B TW I811399B
Authority
TW
Taiwan
Prior art keywords
resin composition
mass
resin
component
group
Prior art date
Application number
TW108125420A
Other languages
Chinese (zh)
Other versions
TW202012535A (en
Inventor
西村嘉生
Original Assignee
日商味之素股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商味之素股份有限公司 filed Critical 日商味之素股份有限公司
Publication of TW202012535A publication Critical patent/TW202012535A/en
Application granted granted Critical
Publication of TWI811399B publication Critical patent/TWI811399B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C08L101/08—Carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

本發明的課題為提供：一種樹脂組成物，其能夠得到介電正切為低、高溫高濕環境試驗後的絕緣可靠性為優異的硬化物；含該樹脂組成物而成的樹脂薄片；具備使用該樹脂組成物形成的絕緣層而成的印刷配線板及半導體裝置。 解決課題的本發明的樹脂組成物，其包含：(A)環氧樹脂、(B)硬化劑、(C)苯乙烯系彈性體及(D-1)具有(甲基)丙烯醯基的樹脂。The object of the present invention is to provide: a resin composition capable of obtaining a cured product with a low dielectric tangent and excellent insulation reliability after a high-temperature and high-humidity environment test; a resin sheet containing the resin composition; and the ability to use the resin composition. Printed wiring boards and semiconductor devices made of an insulating layer formed of the resin composition. The resin composition of the present invention that solves the problem includes: (A) epoxy resin, (B) hardener, (C) styrene elastomer, and (D-1) resin having (meth)acrylyl group .

Description

樹脂組成物resin composition

本發明為關於樹脂組成物。進而為關於含該樹脂組成物而成的樹脂薄片、印刷配線板及半導體裝置。The present invention relates to a resin composition. Furthermore, it relates to resin sheets, printed wiring boards, and semiconductor devices containing the resin composition.

作為印刷配線板之製造技術，已知有藉由在內層電路基板上交替重疊絕緣層與導體層之增層(build-up)方式之製造方法。近年的絕緣層，變得要求能夠降低在高頻下的電信號之損失，而要求著介電正切(dielectric tangent)為低的絕緣層。As a manufacturing technology for printed wiring boards, a build-up manufacturing method in which insulating layers and conductive layers are alternately stacked on an inner circuit board is known. Insulating layers in recent years are required to be able to reduce the loss of electrical signals at high frequencies, and an insulating layer with a low dielectric tangent is required.

作為形成如此般的絕緣層的樹脂組成物，例如，專利文獻1記載著一種樹脂組成物，其包含：(A)末端具有苯乙烯基的分子量800～1500的熱硬化性樹脂、(B)液狀環氧樹脂、(C)苯乙烯系熱可塑性彈性體、(D)填充材及(E)硬化劑，相對於樹脂組成物100質量份，(D)成分為30～70質量份。 [先前技術文獻] [專利文獻]As a resin composition that forms such an insulating layer, for example, Patent Document 1 describes a resin composition containing: (A) a thermosetting resin with a molecular weight of 800 to 1,500 having a styrene group at the terminal; (B) a liquid epoxy resin, (C) styrenic thermoplastic elastomer, (D) filler and (E) hardener, and (D) component is 30 to 70 parts by mass relative to 100 parts by mass of the resin composition. [Prior technical literature] [Patent Document]

[專利文獻1]日本特開2016-147945號公報[Patent Document 1] Japanese Patent Application Publication No. 2016-147945

[發明所欲解決之課題][Problem to be solved by the invention]

本發明人為了得到介電正切為低的絕緣層，對於含有能使樹脂組成物整體低極性化的自由基聚合性化合物而成的樹脂組成物進行了研究。其結果發現下述的新課題：若於樹脂組成物中含有自由基聚合性化合物時，樹脂組成物的硬化物於高溫高濕環境試驗後的絕緣可靠性會劣化。In order to obtain an insulating layer with a low dielectric tangent, the present inventors studied a resin composition containing a radically polymerizable compound that can reduce the polarity of the entire resin composition. As a result, the following new problem was discovered: when a radically polymerizable compound is contained in a resin composition, the insulation reliability of the cured product of the resin composition deteriorates after a high-temperature and high-humidity environment test.

本發明的課題為提供：一種樹脂組成物，其能夠得到介電正切為低、高溫高濕環境試驗後的絕緣可靠性為優異的硬化物；含該樹脂組成物而成的樹脂薄片；具備使用該樹脂組成物形成的絕緣層而成的印刷配線板及半導體裝置。 [解決課題之手段]The object of the present invention is to provide: a resin composition capable of obtaining a cured product with a low dielectric tangent and excellent insulation reliability after a high-temperature and high-humidity environment test; a resin sheet containing the resin composition; and the ability to use the resin composition. Printed wiring boards and semiconductor devices made of an insulating layer formed of the resin composition. [Means to solve the problem]

本發明人為了解決前述的課題經深入研究之結果發現，藉由一種樹脂組成物，除了(A)環氧樹脂、(B)硬化劑以外，其亦包含(C)苯乙烯系彈性體及(D-1)具有(甲基)丙烯醯基的樹脂，可解決本發明的課題，因而完成本發明。進而，本發明人發現，藉由一種樹脂組成物，其包含：(A)環氧樹脂、(B)硬化劑、(C)苯乙烯系彈性體及(D)具有自由基聚合性不飽和基的樹脂，將樹脂組成物以200℃熱硬化90分鐘而得到的硬化物的透濕係數為0g/mm･m2 ･24h以上10g/mm･m2 ･24h以下，可解決本發明的課題，因而完成本發明。 即，本發明包含下述的內容。The inventors of the present invention conducted in-depth research to solve the aforementioned problems and found that a resin composition, in addition to (A) epoxy resin and (B) hardener, also contains (C) styrene-based elastomer and (C) styrene-based elastomer and (B) hardener. D-1) The resin having a (meth)acrylyl group can solve the problems of the present invention, and thus the present invention has been completed. Furthermore, the inventors of the present invention discovered that a resin composition containing: (A) epoxy resin, (B) hardener, (C) styrenic elastomer, and (D) having a radically polymerizable unsaturated group The moisture permeability coefficient of the cured product obtained by thermally curing the resin composition at 200°C for 90 minutes is 0g/mm･m 2 ･24h or more and 10g/mm･m 2 ･24h or less, which can solve the problem of the present invention, Thus, the present invention is completed. That is, the present invention includes the following contents.

[1]. 一種樹脂組成物，其包含： (A)環氧樹脂、 (B)硬化劑、 (C)苯乙烯系彈性體及 (D-1)具有(甲基)丙烯醯基的樹脂。 [2]. 一種樹脂組成物，其包含： (A)環氧樹脂、 (B)硬化劑、 (C)苯乙烯系彈性體及 (D)具有自由基聚合性不飽和基的樹脂， 將樹脂組成物以200℃熱硬化90分鐘而得到的硬化物的透濕係數為0g/mm･m2 ･24h以上10g/mm･m2 ･24h以下。 [3]. 如[2]記載之樹脂組成物，其中，(D)成分包含(D-1)具有(甲基)丙烯醯基的樹脂。 [4]. 如[1]或[3]記載之樹脂組成物，其中，(D-1)成分的數平均分子量為3000以下。 [5]. 如[1]～[4]中任一項記載之樹脂組成物，其中，將樹脂組成物中的樹脂成分設為100質量%時，(C)成分的含量為0.5質量%以上18質量%以下。 [6]. 如[1]～[5]中任一項記載之樹脂組成物，其中，將(C)成分設為100質量%時，(C)成分中包含61質量%以上的苯乙烯單位的含量。 [7]. 如[1]～[6]中任一項記載之樹脂組成物，其中，將樹脂組成物中的不揮發成分設為100質量%時，(B)成分的含量為1質量%以上15質量%以下。 [8]. 如[1]～[7]中任一項記載之樹脂組成物，其中，進一步包含(E)無機填充材。 [9]. 如[8]記載之樹脂組成物，其中，將樹脂組成物中的不揮發成分設為100質量%時，(E)成分的含量為50質量%以上。 [10]. 如[1]～[9]中任一項記載之樹脂組成物，其係絕緣層形成用。 [11]. 如[1]～[10]中任一項記載之樹脂組成物，其係用來形成導體層的絕緣層形成用。 [12]. 如[1]～[11]中任一項記載之樹脂組成物，其係用來以濺鍍或金屬箔來形成導體層的絕緣層形成用。 [13]. 如[1]～[12]中任一項記載之樹脂組成物，其係具有頂部孔徑為45μm以下的通孔的絕緣層形成用。 [14]. 如[1]～[13]中任一項記載之樹脂組成物，其係厚度為20μm以下的絕緣層形成用。 [15]. 一種樹脂薄片，其包含： 支撐體與 設置於該支撐體上的樹脂組成物層， 該樹脂組成物層包含[1]～[14]中任一項記載之樹脂組成物。 [16]. 一種包含絕緣層的印刷配線板，該絕緣層係藉由[1]～[14]中任一項記載之樹脂組成物的硬化物所形成者。 [17]. 一種半導體裝置，其包含[16]記載之印刷配線板。 [發明的效果][1]. A resin composition containing: (A) epoxy resin, (B) hardener, (C) styrene elastomer, and (D-1) resin having a (meth)acrylyl group. [2]. A resin composition containing: (A) epoxy resin, (B) hardener, (C) styrenic elastomer, and (D) resin having a radically polymerizable unsaturated group, the resin The moisture permeability coefficient of the cured product obtained by thermally curing the composition at 200°C for 90 minutes is 0 g/mm･m 2 ･24h or more and 10 g/mm･m 2 ･24h or less. [3]. The resin composition according to [2], wherein the component (D) contains (D-1) a resin having a (meth)acryl group. [4]. The resin composition according to [1] or [3], wherein the number average molecular weight of the component (D-1) is 3,000 or less. [5]. The resin composition according to any one of [1] to [4], wherein the content of component (C) is 0.5 mass% or more when the resin component in the resin composition is 100 mass%. 18% by mass or less. [6]. The resin composition according to any one of [1] to [5], wherein the component (C) contains 61 mass% or more of styrene units when the component (C) is 100 mass%. content. [7]. The resin composition according to any one of [1] to [6], wherein the content of component (B) is 1 mass% when the non-volatile component in the resin composition is 100 mass%. Above 15% by mass and below. [8]. The resin composition according to any one of [1] to [7], further comprising (E) an inorganic filler. [9]. The resin composition according to [8], wherein the content of component (E) is 50 mass% or more when the non-volatile components in the resin composition are 100 mass%. [10]. The resin composition according to any one of [1] to [9], which is used for forming an insulating layer. [11]. The resin composition according to any one of [1] to [10], which is used to form an insulating layer for forming a conductor layer. [12]. The resin composition according to any one of [1] to [11], which is used to form an insulating layer for forming a conductor layer by sputtering or metal foil. [13]. The resin composition according to any one of [1] to [12], which is used for forming an insulating layer having a through hole with a top hole diameter of 45 μm or less. [14]. The resin composition according to any one of [1] to [13], which is used for forming an insulating layer with a thickness of 20 μm or less. [15]. A resin sheet comprising: a support and a resin composition layer provided on the support, the resin composition layer including the resin composition described in any one of [1] to [14]. [16]. A printed wiring board including an insulating layer formed from a cured product of the resin composition according to any one of [1] to [14]. [17]. A semiconductor device including the printed wiring board described in [16]. [Effects of the invention]

藉由本發明係可提供：一種樹脂組成物，其能夠得到介電正切為低、高溫高濕環境試驗後的絕緣可靠性為優異的硬化物；含該樹脂組成物而成的樹脂薄片；具備使用該樹脂組成物形成的絕緣層而成的印刷配線板及半導體裝置。The present invention can provide: a resin composition capable of obtaining a cured product with a low dielectric tangent and excellent insulation reliability after a high-temperature and high-humidity environment test; a resin sheet containing the resin composition; and a device that can be used Printed wiring boards and semiconductor devices made of an insulating layer formed of the resin composition.

[實施發明之最佳形態][The best way to implement the invention]

以下為表示實施形態及示例物，來對於本發明進行詳細說明。但，本發明並不受以下所舉出的實施形態及示例物的限定，可在不脫離本發明申請專利範圍及其均等範圍的範圍內任意地變更而實施。The present invention will be described in detail below by showing embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and can be arbitrarily modified and implemented without departing from the patentable scope of the present invention and its equivalent range.

[樹脂組成物] 本發明的第一實施形態的樹脂組成物，其包含：(A)環氧樹脂、(B)硬化劑、(C)苯乙烯系彈性體及(D-1)具有(甲基)丙烯醯基的樹脂。藉由使用如此般的樹脂組成物，能夠得到介電正切為低、高溫高濕環境試驗後的絕緣可靠性為優異的硬化物。進而，藉由使用如此般的樹脂組成物，能夠提高與導體層之間的剝離強度。[Resin composition] The resin composition according to the first embodiment of the present invention contains: (A) epoxy resin, (B) hardener, (C) styrene elastomer, and (D-1) having (meth)acrylyl group of resin. By using such a resin composition, it is possible to obtain a cured product that has a low dielectric tangent and excellent insulation reliability after a high-temperature and high-humidity environment test. Furthermore, by using such a resin composition, the peeling strength from the conductor layer can be improved.

第一實施形態的樹脂組成物亦可進一步包含任意的成分來與(A)～(D-1)成分組合。作為任意的成分，可舉例如(D-2)具有乙烯基苯基的樹脂、(E)無機填充材、(F)硬化促進劑、(G)聚合起始劑及(H)其他的添加劑等。The resin composition of the first embodiment may further contain optional components in combination with the components (A) to (D-1). Examples of optional components include (D-2) vinyl phenyl group-containing resin, (E) inorganic filler, (F) hardening accelerator, (G) polymerization initiator, (H) other additives, etc. .

又，本發明的第二實施形態的樹脂組成物，其包含：(A)環氧樹脂、(B)硬化劑、(C)苯乙烯系彈性體及(D)具有自由基聚合性不飽和基的樹脂，將樹脂組成物以200℃熱硬化90分鐘而得到的硬化物的透濕係數為0g/mm･m2 ･24h以上10g/mm･m2 ･24h以下。藉由使用如此般的樹脂組成物，能夠得到介電正切為低、高溫高濕環境試驗後的絕緣可靠性為優異的硬化物。進而，藉由使用如此般的樹脂組成物，能夠提高與導體層之間的剝離強度。Furthermore, the resin composition according to the second embodiment of the present invention contains: (A) epoxy resin, (B) hardener, (C) styrenic elastomer, and (D) radically polymerizable unsaturated group The moisture permeability coefficient of the cured product obtained by thermally curing the resin composition at 200°C for 90 minutes is 0g/mm･m 2 ･24h or more and 10g/mm･m 2 ･24h or less. By using such a resin composition, it is possible to obtain a cured product that has a low dielectric tangent and excellent insulation reliability after a high-temperature and high-humidity environment test. Furthermore, by using such a resin composition, the peeling strength from the conductor layer can be improved.

第二實施形態的樹脂組成物亦可進一步包含任意的成分來與(A)～(D)成分組合。作為任意的成分，可舉例如(E)無機填充材、(F)硬化促進劑、(G)聚合起始劑及(H)其他的添加劑等。The resin composition of the second embodiment may further contain optional components in combination with the components (A) to (D). Examples of optional components include (E) inorganic filler, (F) hardening accelerator, (G) polymerization initiator, (H) other additives, and the like.

在此，(D-1)具有(甲基)丙烯醯基的樹脂及(D-2)具有乙烯基苯基的樹脂係皆被包含於「(D)具有自由基聚合性不飽和基的樹脂」之中。又，有將第一實施形態的樹脂組成物及第二實施形態的樹脂組成物總稱為「樹脂組成物」之情形。以下為對於樹脂組成物中所包含的各成分進行詳細說明。Here, (D-1) The resin having a (meth)acrylyl group and (D-2) The resin having a vinylphenyl group are both included in "(D) Resin having a radically polymerizable unsaturated group ” among. In addition, the resin composition of the first embodiment and the resin composition of the second embodiment may be collectively referred to as "resin composition". The following is a detailed description of each component contained in the resin composition.

＜(A)環氧樹脂＞ 作為(A)環氧樹脂，可舉例如聯二甲苯酚(bixylenol)型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、雙環戊二烯型環氧樹脂、三元酚型環氧樹脂、萘酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、tert-丁基-兒茶酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、縮水甘油胺型環氧樹脂、縮水甘油酯型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、線狀脂肪族環氧樹脂、具有丁二烯構造的環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂、含有螺環的環氧樹脂、環己烷型環氧樹脂、環己烷二甲醇型環氧樹脂、伸萘基醚(naphthylene ether)型環氧樹脂、三羥甲基型環氧樹脂、四苯基乙烷型環氧樹脂等。環氧樹脂係可單獨使用1種類、或可組合2種類以上來使用。＜(A) Epoxy resin＞ Examples of (A) epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol AF. type epoxy resin, dicyclopentadiene type epoxy resin, trihydric phenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy Resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin Oxygen resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane-type epoxy resin , cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. One type of epoxy resin can be used alone, or two or more types can be used in combination.

樹脂組成物中，作為(A)環氧樹脂，以包含於1分子中具有2個以上的環氧基的環氧樹脂為較佳。就可顯著地得到本發明所期望之效果之觀點而言，相對於(A)環氧樹脂的不揮發成分100質量%，於1分子中具有2個以上的環氧基的環氧樹脂的比例係較佳為50質量%以上，又較佳為60質量%以上，特佳為70質量%以上。In the resin composition, (A) the epoxy resin is preferably an epoxy resin containing two or more epoxy groups per molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the ratio of the epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of the non-volatile component of the epoxy resin (A) The content is preferably 50 mass% or more, more preferably 60 mass% or more, and particularly preferably 70 mass% or more.

環氧樹脂係可分類成在溫度20℃下液狀的環氧樹脂(以下有時稱為「液狀環氧樹脂」)、與在溫度20℃下固體狀的環氧樹脂(有時稱為「固體狀環氧樹脂」)。樹脂組成物中，作為(A)環氧樹脂係可僅包含液狀環氧樹脂，亦可僅包含固體狀環氧樹脂，亦可組合包含液狀環氧樹脂與固體狀環氧樹脂為較佳。但就可顯著地得到本發明所期望之效果之觀點而言，以僅包含固體狀環氧樹脂為佳。Epoxy resins can be classified into epoxy resins that are liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (sometimes referred to as "liquid epoxy resins"). "Solid epoxy resin"). In the resin composition, (A) the epoxy resin system may contain only a liquid epoxy resin, or may contain only a solid epoxy resin, or it may preferably contain a combination of a liquid epoxy resin and a solid epoxy resin. . However, from the viewpoint of significantly obtaining the desired effects of the present invention, it is preferable to contain only solid epoxy resin.

作為固體狀環氧樹脂，較佳為於1分子中具有3個以上的環氧基的固體狀環氧樹脂，又較佳為於1分子中具有3個以上的環氧基的芳香族系的固體狀環氧樹脂。As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups per molecule is preferred, and an aromatic resin having three or more epoxy groups per molecule is more preferred. Solid epoxy resin.

作為固體狀環氧樹脂，較佳為聯二甲苯酚型環氧樹脂、萘型環氧樹脂、萘型4官能環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙環戊二烯型環氧樹脂、三元酚型環氧樹脂、萘酚型環氧樹脂、聯苯型環氧樹脂、伸萘基醚型環氧樹脂、蒽型環氧樹脂、雙酚A型環氧樹脂、雙酚AF型環氧樹脂、四苯基乙烷型環氧樹脂，又較佳為萘型環氧樹脂。As the solid epoxy resin, preferred are dixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, and dicyclopentadiene-type epoxy resin. , Trihydric phenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type Epoxy resin, tetraphenylethane type epoxy resin, and preferably naphthalene type epoxy resin.

固體狀環氧樹脂的具體例，可舉出DIC公司製的「HP4032H」(萘型環氧樹脂)；DIC公司製的「HP-4700」、「HP-4710」(萘型4官能環氧樹脂)；DIC公司製的「N-690」(甲酚酚醛清漆型環氧樹脂)；DIC公司製的「N-695」(甲酚酚醛清漆型環氧樹脂)；DIC公司製的「HP-7200」、「HP-7200HH」、「HP-7200H」(雙環戊二烯型環氧樹脂)；DIC公司製的「EXA-7311」、「EXA-7311-G3」、「EXA-7311-G4」、「EXA-7311-G4S」、「HP6000」(伸萘基醚型環氧樹脂)；日本化藥公司製的「EPPN-502H」(三元酚型環氧樹脂)；日本化藥公司製的「NC7000L」(萘酚酚醛清漆型環氧樹脂)；日本化藥公司製的「NC3000H」、「NC3000」、「NC3000L」、「NC3100」(聯苯型環氧樹脂)；新日鐵住金化學公司製的「ESN475V」(萘酚型環氧樹脂)；新日鐵住金化學公司製的「ESN485」(萘酚酚醛清漆型環氧樹脂)；三菱化學公司製的「YX4000H」、「YX4000」、「YL6121」(聯苯型環氧樹脂)；三菱化學公司製的「YX4000HK」(聯二甲苯酚型環氧樹脂)；三菱化學公司製的「YX8800」(蒽型環氧樹脂)；OSAKA Gas chemical公司製的「PG-100」、「CG-500」；三菱化學公司製的「YL7760」(雙酚AF型環氧樹脂)；三菱化學公司製的「YL7800」(茀型環氧樹脂)；三菱化學公司製的「jER1010」(固體狀雙酚A型環氧樹脂)；三菱化學公司製的「jER1031S」(四苯基乙烷型環氧樹脂)等。該等係可單獨使用1種類、或可組合2種類以上來使用。Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC Corporation ); "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200" manufactured by DIC Corporation ", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" made by DIC Corporation, "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (trihydric phenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "Nihon Kayaku Co., Ltd." "NC7000L" (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Chemical Co., Ltd.; manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. "ESN475V" (naphthol type epoxy resin); "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.; "YX4000H", "YX4000", "YL6121" manufactured by Mitsubishi Chemical Corporation ” (biphenyl-type epoxy resin); “YX4000HK” (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; “YX8800” (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; manufactured by OSAKA Gas Chemical Co., Ltd. "PG-100", "CG-500"; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (buck type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These can be used individually by 1 type, or can be used in combination of 2 or more types.

作為液狀環氧樹脂，較佳為於1分子中具有2個以上的環氧基的液狀環氧樹脂。As the liquid epoxy resin, one having two or more epoxy groups per molecule is preferred.

作為液狀環氧樹脂，較佳為雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂、萘型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、苯酚酚醛清漆型環氧樹脂、具有酯骨架的脂環式環氧樹脂、環己烷型環氧樹脂、環己烷二甲醇型環氧樹脂、縮水甘油胺型環氧樹脂及具有丁二烯構造的環氧樹脂，又較佳為雙酚A型環氧樹脂、雙酚F型環氧樹脂。As the liquid epoxy resin, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, and glycidyl ester type epoxy resin. Amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin And epoxy resins with butadiene structure, preferably bisphenol A type epoxy resin and bisphenol F type epoxy resin.

作為液狀環氧樹脂的具體例，可舉出DIC公司製的「HP4032」、「HP4032D」、「HP4032SS」(萘型環氧樹脂)；三菱化學公司製的「828US」、「jER828EL」、「825」、「Epikote 828EL」(雙酚A型環氧樹脂)；三菱化學公司製的「jER807」、「1750」(雙酚F型環氧樹脂)；三菱化學公司製的「jER152」(苯酚酚醛清漆型環氧樹脂)；三菱化學公司製的「630」、「630LSD」(縮水甘油胺型環氧樹脂)；新日鐵住金化學公司製的「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂的混合品)；Nagasechemtex公司製的「EX-721」(縮水甘油酯型環氧樹脂)；Daicel公司製的「CELOXIDE2021P」(具有酯骨架的脂環式環氧樹脂)；Daicel公司製的「PB-3600」(具有丁二烯構造的環氧樹脂)；新日鐵住金化學公司製的「ZX1658」、「ZX1658GS」(液狀1,4-縮水甘油環己烷型環氧樹脂)等。該等係可單獨使用1種類、或可組合2種類以上來使用。Specific examples of liquid epoxy resins include "HP4032", "HP4032D" and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL" and " 825", "Epikote 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation's "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical Corporation's "jER152" (phenol novolac Varnish type epoxy resin); "630" and "630LSD" (glycidyl amine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A type epoxy resin and bisphenol A type epoxy resin) manufactured by Nippon Steel and Sumitomo Metal Chemical Corporation Mixed product of phenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagasechemtex Corporation; "CELOXIDE2021P" (alicyclic epoxy resin with an ester skeleton) manufactured by Daicel Corporation; "PB-3600" manufactured by Daicel Co., Ltd. (epoxy resin with butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel and Sumitomo Metal Chemical Co., Ltd. (liquid 1,4-glycidyl cyclohexane type cyclic resin) Oxygen resin) etc. These can be used individually by 1 type, or can be used in combination of 2 or more types.

作為(A)環氧樹脂若組合液狀環氧樹脂與固體狀環氧樹脂來使用之情形時，該等的量比(液狀環氧樹脂：固體狀環氧樹脂)係以質量比計，較佳為1：1～1：20，又較佳為1：1.5～1：15，特佳為1：2～1：10。藉由將液狀環氧樹脂與固體狀環氧樹脂的量比設為上述範圍，從而可顯著地得到本發明所期望之效果。進而，通常若以樹脂薄片的形態來使用時，可獲得適度的黏著性。又，通常若以樹脂薄片的形態來使用時，因可得到充分的可撓性，故操作性為提升。進而，通常係能夠得到具有充分的破斷強度的硬化物。 When the epoxy resin (A) is used in combination with a liquid epoxy resin and a solid epoxy resin, the quantitative ratio (liquid epoxy resin: solid epoxy resin) is based on the mass ratio, Preferably it is 1:1～1:20, more preferably 1:1.5～1:15, particularly preferably 1:2～1:10. By setting the quantitative ratio of the liquid epoxy resin to the solid epoxy resin within the above range, the desired effects of the present invention can be significantly obtained. Furthermore, when used in the form of a resin sheet, moderate adhesion can generally be obtained. In addition, if it is generally used in the form of a resin sheet, sufficient flexibility can be obtained, so the operability is improved. Furthermore, a hardened material having sufficient breaking strength can usually be obtained.

(A)環氧樹脂的環氧當量係較佳為50g/eq.~5000g/eq.，又較佳為50g/eq.~3000g/eq.，更佳為80g/eq.~2000g/eq.，又更佳為110g/eq.~1000g/eq.。藉由成為該範圍，從而使樹脂組成物層的硬化物的交聯密度變得充分，故能夠獲得表面粗糙度為較小的絕緣層。環氧當量係包含1當量的環氧基的環氧樹脂的質量。該環氧當量係可根據JIS K7236來進行測定。 (A) The epoxy equivalent of the epoxy resin is preferably 50g/eq.~5000g/eq., more preferably 50g/eq.~3000g/eq., and more preferably 80g/eq.~2000g/eq. , and preferably 110g/eq.~1000g/eq. By entering this range, the crosslinking density of the cured product of the resin composition layer becomes sufficient, so that an insulating layer with a small surface roughness can be obtained. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured based on JIS K7236.

(A)環氧樹脂的重量平均分子量(Mw)，就可顯著地得到本發明所期望之效果之觀點而言，較佳為100~5000，又較佳為250~3000，更佳為400~1500。 (A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 400 in order to significantly obtain the desired effects of the present invention. 1500.

樹脂的重量平均分子量係可藉由凝膠滲透層析(GPC)法，而以作為聚苯乙烯換算的值來測得。 The weight average molecular weight of the resin can be measured as a value converted to polystyrene by gel permeation chromatography (GPC).

(A)環氧樹脂的含量，就可得到展現出良好的機械強度、高溫高濕環境試驗後的絕緣可靠性的絕緣層之觀點而言，將樹脂組成物中的不揮發成分設為100質量%時，較佳為1質量%以上，又較佳為2質量%以上，更佳為3質量%以上。環氧樹脂的含量的上限，就可顯著地得到本發明所期望之效果之觀點而言，較佳為15質量%以下，又較佳為10質量%以下，特佳為5質量%以下。尚，本發明中，樹脂組成物中的各成分的含量，如無特別說明，係將樹脂組成物中的不揮發成分設為100質量%時的值。 (A) The content of the epoxy resin. From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability after a high-temperature and high-humidity environment test, the non-volatile component in the resin composition is set to 100 mass %, it is preferably 1 mass% or more, more preferably 2 mass% or more, and more preferably 3 mass% or more. The upper limit of the content of the epoxy resin is preferably 15 mass% or less, more preferably 10 mass% or less, and particularly preferably 5 mass% or less, from the viewpoint of significantly obtaining the desired effects of the present invention. Furthermore, in the present invention, the content of each component in the resin composition is the value when the non-volatile component in the resin composition is 100% by mass, unless otherwise specified.

<(B)硬化劑> <(B) Hardener>

樹脂組成物包含硬化劑來作為(B)成分。通常而言，(B)硬化劑為具有與(A)環氧樹脂進行反應來使樹脂組成物硬化之機能。 The resin composition contains a hardener as (B) component. Generally speaking, (B) hardener has the function of reacting with (A) epoxy resin to harden the resin composition.

作為(B)硬化劑，可舉例如活性酯系硬化劑、酚(phenol)系硬化劑、萘酚(naphthol)系硬化劑、苯并噁嗪(benzoxazine)系硬化劑、氰酸酯系硬化劑、碳二亞胺(carbodiimide)系硬化劑、胺系硬化劑、酸酐系硬化劑等。(B)硬化劑係可單獨使用1種類、或可組合2種類以上來使用。 Examples of the (B) curing agent include active ester curing agents, phenol curing agents, naphthol curing agents, benzoxazine curing agents, and cyanate ester curing agents. , carbodiimide (carbodiimide) hardener, amine hardener, acid anhydride hardener, etc. (B) The hardening agent can be used individually by 1 type, or can be used in combination of 2 or more types.

作為活性酯系硬化劑，可使用於1分子中具有1個以上的活性酯基的化合物。其中，作為活性酯系硬化劑，較佳為苯酚酯類、苯硫酚酯類、N-羥基胺酯類、雜環羥基化合物的酯類等的於1分子中具有2個以上的反應活性為高的酯基的化合物。該活性酯系硬化劑係以藉由羧酸化合物及/或硫代羧酸化合物與羥基化合物及/或硫醇化合物的縮合反應而得者為較佳。特別是就耐熱性提升之觀點而言，以由羧酸化合物與羥基化合物所得到的活性酯系硬化劑為較佳，以由羧酸化合物與苯酚化合物及/或萘酚化合物所得到的活性酯系硬化劑為又較佳。 As the active ester type curing agent, a compound having one or more active ester groups per molecule can be used. Among them, as the active ester-based hardener, preferred are phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxyl compounds, etc., which have two or more reactive activities per molecule. Compounds with high ester base. The active ester hardener is preferably obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester hardener obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is preferred. It is better to use hardener.

作為羧酸化合物，可舉例如苯甲酸、乙酸、琥珀酸、馬來酸、伊康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、焦蜜石酸等。 Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromelonic acid, and the like.

作為苯酚化合物或萘酚化合物，可舉例如氫醌、間苯二酚、雙酚A、雙酚F、雙酚S、還原酚酞、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、苯酚、o-甲酚、m-甲酚、p-甲酚、兒茶酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基苯甲酮、三羥基苯甲酮、四羥基苯甲酮、間苯三酚、苯三酚、雙環戊二烯型二苯酚化合物、苯酚酚醛清漆等。於此，所謂的「雙環戊二烯型二苯酚化合物」，係指雙環戊二烯1分子中縮合有苯酚2分子而得到的二苯酚化合物。Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, reduced phenolphthalein, methylated bisphenol A, methylated bisphenol F, methyl Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene Naphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, phloroglucinol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. . Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol into one molecule of dicyclopentadiene.

作為活性酯系硬化劑的較佳的具體例，可舉出包含雙環戊二烯型二苯酚構造的活性酯系硬化劑、包含萘構造的活性酯系硬化劑、包含苯酚酚醛清漆的乙醯化物的活性酯系硬化劑、包含苯酚酚醛清漆的苯甲醯化物的活性酯系硬化劑。其中，又較佳為包含萘構造的活性酯系硬化劑、包含雙環戊二烯型二苯酚構造的活性酯系硬化劑。所謂的「雙環戊二烯型二苯酚構造」，係表示由伸苯基-二伸環戊基-伸苯基所成的2價的構造單位。Preferable specific examples of the active ester-based hardener include an active ester-based hardener containing a dicyclopentadiene-type diphenol structure, an active ester-based hardener containing a naphthalene structure, and an acetate containing phenol novolak. An active ester hardener, an active ester hardener containing a benzyl compound of phenol novolac. Among these, an active ester-based hardener containing a naphthalene structure and an active ester-based hardening agent containing a dicyclopentadiene-type diphenol structure are more preferred. The so-called "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene group.

作為活性酯系硬化劑的市售品，可舉例：作為包含雙環戊二烯型二苯酚構造的活性酯系硬化劑的「EXB9451」、「EXB9460」、「EXB9460S」、「HPC8000-65T」、「HPC8000H-65TM」、「EXB8000L-65TM」、「EXB8150-65T」(DIC公司製)；作為包含萘構造的活性酯系硬化劑的「EXB9416-70BK」(DIC公司製)；作為包含苯酚酚醛清漆的乙醯化物的活性酯系硬化劑的「DC808」(三菱化學公司製)；作為包含苯酚酚醛清漆的苯甲醯化物的活性酯系硬化劑的「YLH1026」(三菱化學公司製)；作為苯酚酚醛清漆的乙醯化物的活性酯系硬化劑的「DC808」(三菱化學公司製)；作為苯酚酚醛清漆的苯甲醯化物的活性酯系硬化劑的「YLH1026」(三菱化學公司製)、「YLH1030」(三菱化學公司製)、「YLH1048」(三菱化學公司製)等。Examples of commercially available active ester hardeners include: "EXB9451", "EXB9460", "EXB9460S", "HPC8000-65T", "EXB9451", "EXB9460", "EXB9460S", " HPC8000H-65TM", "EXB8000L-65TM", "EXB8150-65T" (manufactured by DIC Corporation); "EXB9416-70BK" (manufactured by DIC Corporation) which is an active ester hardener containing a naphthalene structure; and which is a phenol novolak containing "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based hardener of an acetate compound; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based hardener of a benzyl compound containing phenol novolac; as a phenol novolac "DC808" (manufactured by Mitsubishi Chemical Corporation), an active ester-based hardener of acetate compounds in varnish; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), which is an active ester-based hardener of benzyl compounds in phenol novolaks ” (manufactured by Mitsubishi Chemical Corporation), “YLH1048” (manufactured by Mitsubishi Chemical Corporation), etc.

作為酚系硬化劑及萘酚系硬化劑，就耐熱性及耐水性之觀點而言，以具有酚醛清漆構造者為較佳。又，就與導體層的密著性之觀點而言，以含氮酚系硬化劑為較佳，以含有三嗪骨架的酚系硬化劑為又較佳。As the phenol-based hardener and the naphthol-based hardener, those having a novolak structure are preferred from the viewpoint of heat resistance and water resistance. Furthermore, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based hardening agent is preferred, and a phenol-based hardening agent containing a triazine skeleton is further preferred.

作為酚系硬化劑及萘酚系硬化劑的具體例，可舉例如明和化成公司製的「MEH-7700」、「MEH-7810」、「MEH-7851」；日本化藥公司製的「NHN」、「CBN」、「GPH」；新日鐵住金化學公司製的「SN170」、「SN180」、「SN190」、「SN475」、「SN485」、「SN495」、「SN-495V」、「SN375」；DIC公司製的「TD-2090」、「LA-7052」、「LA-7054」、「LA-1356」、「LA-3018-50P」、「EXB-9500」等。Specific examples of phenol-based hardeners and naphthol-based hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd.; and "NHN" manufactured by Nippon Kayaku Co., Ltd. , "CBN", "GPH"; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. ; "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc. made by DIC Corporation.

苯并噁嗪系硬化劑的具體例，可舉出JFE Chemical公司製的「ODA-BOZ」、昭和高分子公司製的「HFB2006M」、四國化成工業公司製的「P-d」、「F-a」。Specific examples of the benzoxazine-based hardener include "ODA-BOZ" manufactured by JFE Chemical Co., Ltd., "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

作為氰酸酯系硬化劑，可舉例如雙酚A二氰酸酯、多元酚氰酸酯、寡(3-亞甲基-1,5-伸苯基氰酸酯)、4,4’-亞甲基雙(2,6-二甲基苯基氰酸酯)、4,4’-亞乙基二苯基二氰酸酯、六氟雙酚A二氰酸酯、2,2-雙(4-氰酸酯)苯基丙烷、1,1-雙(4-氰酸酯苯基甲烷)、雙(4-氰酸酯-3,5-二甲基苯基)甲烷、1,3-雙(4-氰酸酯苯基-1-(甲基亞乙基))苯、雙(4-氰酸酯苯基)硫醚及雙(4-氰酸酯苯基)醚等的2官能氰酸酯樹脂；由苯酚酚醛清漆及甲酚酚醛清漆等所衍生的多官能氰酸酯樹脂；該等氰酸酯樹脂被一部分三嗪化的預聚合物等。作為氰酸酯系硬化劑的具體例，可舉出LONZA Japan公司製的「PT30」及「PT60」(苯酚酚醛清漆型多官能氰酸酯樹脂)、「ULL-950S」(多官能氰酸酯樹脂)、「BA230」、「BA230S75」(雙酚A二氰酸酯的一部分或全部被三嗪化而成為三量體的預聚合物)等。Examples of the cyanate-based hardener include bisphenol A dicyanate, polyhydric phenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), and 4,4'- Methylene bis (2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3 - Bis(4-cyanatephenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide and bis(4-cyanatephenyl)ether, etc. 2 Functional cyanate ester resin; multifunctional cyanate ester resin derived from phenol novolak and cresol novolac; prepolymers in which these cyanate ester resins are partially triazinized, etc. Specific examples of cyanate ester-based hardeners include "PT30" and "PT60" (phenol novolak type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin) manufactured by LONZA Japan Resin), "BA230", "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazinated to form a tripartite), etc.

作為碳二亞胺系硬化劑的具體例，可舉出Nisshinbo chemical公司製的「V-03」、「V-05」、「V-07」、「V-09」；Rhein Chemie公司製的Stabaxol(註冊商標)P等。Specific examples of carbodiimide-based hardeners include "V-03", "V-05", "V-07", and "V-09" manufactured by Nisshinbo Chemical Co., Ltd.; Stabaxol manufactured by Rhein Chemie Co., Ltd. (Registered Trademark) P et al.

作為胺系硬化劑，可舉出於1分子內具有1個以上的胺基而成的硬化劑，可舉例如脂肪族胺類、聚醚胺類、脂環式胺類、芳香族胺類等，其中，就達成本發明所期望之效果之觀點而言，較佳為芳香族胺類。胺系硬化劑，較佳為第1級胺或第2級胺，又較佳為第1級胺。作為胺系硬化劑的具體例，可舉出4,4’-亞甲基雙(2,6-二甲基苯胺)、二苯基二胺基碸、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基碸、3,3’-二胺基二苯基碸、m-苯二胺、m-二甲苯二胺、二乙基甲苯二胺、4,4’-二胺基二苯基醚、3,3’-二甲基-4,4’-二胺基聯苯、2,2’-二甲基-4,4’-二胺基聯苯、3,3’-二羥基聯苯胺、2,2-雙(3-胺基-4-羥基苯基)丙烷、3,3-二甲基-5,5-二乙基-4,4-二苯基甲烷二胺、2,2-雙(4-胺基苯基)丙烷、2,2-雙(4-(4-胺基苯氧基)苯基)丙烷、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、4,4’-雙(4-胺基苯氧基)聯苯、雙(4-(4-胺基苯氧基)苯基)碸、雙(4-(3-胺基苯氧基)苯基)碸等。胺系硬化劑亦可使用市售品，可舉例如日本化藥公司製的「KAYABOND C-200S」、「KAYABOND C-100」、「KAYAHARD A-A」、「KAYAHARD A-B」、「KAYAHARD A-S」、三菱化學公司製的「Epicure W」等。Examples of the amine-based curing agent include those having one or more amine groups per molecule. Examples include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. , among them, from the viewpoint of achieving the desired effects of the present invention, aromatic amines are preferred. The amine-based hardener is preferably a first-level amine or a second-level amine, and more preferably a first-level amine. Specific examples of the amine-based hardener include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminotriene, and 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylenediamine, diethyltoluenediamine, 4 ,4'-Diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl ether Benzene, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4 -Diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis (3-Aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis( 4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sine, bis(4-(3-aminophenoxy)phenyl)sine, etc. Commercially available amine hardeners can also be used, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd., Mitsubishi "Epicure W" produced by a chemical company, etc.

作為酸酐系硬化劑，可舉出於1分子內具有1個以上的酸酐基而成的硬化劑。作為酸酐系硬化劑的具體例，可舉出鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、甲基納迪克酸酐、氫化甲基納迪克酸酐、三烷基四氫鄰苯二甲酸酐、十二烯基琥珀酸酐、5-(2,5-二側氧基四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、偏苯三酸酐、1,2,4,5-苯四酸酐、二苯甲酮四羧酸二酐、聯苯四羧酸二酐、萘四羧酸二酐、氧基二鄰苯二甲酸二酐、3,3’-4,4’-二苯基碸四羧酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二側氧基-3-呋喃基)-萘并[1,2-C]呋喃-1,3-二酮、乙二醇雙(無水偏苯三甲酸酯)、苯乙烯與馬來酸共聚合而成的苯乙烯･馬來酸樹脂等的聚合物型的酸酐等。Examples of the acid anhydride-based curing agent include those having one or more acid anhydride groups per molecule. Specific examples of the acid anhydride-based hardener include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Dicarboxylic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-di-oxytetrahydro-3 -Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl Tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyltetracarboxylic dianhydride, 1,3,3a,4 ,5,9b-hexahydro-5-(tetrahydro-2,5-bisoxy-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol Polymeric acid anhydrides such as bis(anhydrous trimellitate) and styrene maleic acid resin copolymerized with styrene and maleic acid.

上述之中，就可顯著地得到本發明所期望之效果之觀點而言，作為(B)硬化劑較佳為選自酚系硬化劑、活性酯系硬化劑及碳二亞胺系硬化劑中的1種以上。Among the above, the curing agent (B) is preferably selected from the group consisting of phenol-based curing agents, active ester-based curing agents, and carbodiimide-based curing agents from the viewpoint of significantly obtaining the desired effects of the present invention. More than 1 species.

(A)環氧樹脂與(B)硬化劑的量比，以[(A)成分的環氧基的合計數]：[(B)硬化劑的反應基的合計數]的比率計算，較佳為1：0.01～1：20的範圍，又較佳為1：0.05～1：10，更佳為1：0.1～1：8。於此，所謂的「(A)環氧樹脂的環氧基數」，係指將樹脂組成物中存在的(A)環氧樹脂的不揮發成分的質量除以環氧當量的值予以全部合計所得之值。又，所謂的「(B)硬化劑的活性基數」，係指將樹脂組成物中存在的(B)硬化劑的不揮發成分的質量除以活性基當量的值予以全部合計所得之值。藉由將(A)環氧樹脂與(B)硬化劑的量比設為上述範圍內，能夠顯著地得到本發明所期望之效果，進而，通常係可更提升樹脂組成物層的硬化物的耐熱性。The amount ratio of (A) epoxy resin to (B) hardener is preferably calculated as the ratio of [the total number of epoxy groups in component (A)]: [the total number of reactive groups in (B) hardener]. It is in the range of 1:0.01 to 1:20, preferably 1:0.05 to 1:10, more preferably 1:0.1 to 1:8. Here, the "epoxy group number of (A) epoxy resin" refers to the total value obtained by dividing the mass of non-volatile components of (A) epoxy resin present in the resin composition by the epoxy equivalent. value. In addition, the "number of active groups of (B) hardener" refers to a value obtained by dividing the mass of the non-volatile components of (B) hardener present in the resin composition by the active group equivalent and summing all the values. By setting the amount ratio of (A) epoxy resin to (B) hardener within the above range, the desired effects of the present invention can be significantly obtained, and in general, the cured product of the resin composition layer can be further improved. Heat resistance.

(B)硬化劑的含量，就可顯著地得到本發明所期望之效果之觀點而言，相對於樹脂組成物中的不揮發成分100質量%，較佳為0.1質量%以上，又較佳為0.3質量%以上，更佳為0.5質量%以上；較佳為20質量%以下，又較佳為15質量%以下，更佳為10質量%以下。(B) The content of the hardener is preferably 0.1 mass% or more based on 100 mass% of the non-volatile components in the resin composition, and more preferably 0.3 mass% or more, more preferably 0.5 mass% or more; more preferably 20 mass% or less, more preferably 15 mass% or less, more preferably 10 mass% or less.

＜(C)苯乙烯系彈性體＞ 樹脂組成物含有(C)苯乙烯系彈性體。通常而言，(C)苯乙烯系彈性體、與(A)環氧樹脂、(B)硬化劑及(D-1)具有(甲基)丙烯醯基的樹脂的相溶性為高。因此，可抑制(A)成分及(B)成分、與(D-1)成分的相分離。因而，由於可抑制水容易浸入的相界面的產生，故能夠得到高溫高濕環境試驗後的絕緣可靠性為優異的硬化物。又，可使透濕係數調整為較低。＜(C) Styrenic elastomer＞ The resin composition contains (C) styrene-based elastomer. Generally speaking, (C) styrene-based elastomer has high compatibility with (A) epoxy resin, (B) curing agent, and (D-1) resin having a (meth)acryl group. Therefore, phase separation of component (A), component (B), and component (D-1) can be suppressed. Therefore, since the generation of a phase interface into which water can easily penetrate can be suppressed, a cured product having excellent insulation reliability after a high-temperature and high-humidity environment test can be obtained. In addition, the moisture permeability coefficient can be adjusted to be low.

作為(C)苯乙烯系彈性體，可使用包含重複單位(苯乙烯單位)的任意的彈性體，前述重複單位具有將苯乙烯聚合而得到的構造。(C)苯乙烯系彈性體亦可為共聚物，其係包含和前述的苯乙烯單位為不同的任意的重複單位來與苯乙烯單位組合而成的共聚物。As (C) the styrenic elastomer, any elastomer containing a repeating unit (styrene unit) having a structure obtained by polymerizing styrene can be used. (C) The styrene-based elastomer may be a copolymer containing an arbitrary repeating unit different from the aforementioned styrene unit combined with a styrene unit.

作為任意的重複單位，可舉例如：具有將共軛二烯聚合而得到的構造的重複單位(共軛二烯單位)、具有將前述重複單位氫化而得到的構造的重複單位(氫化共軛二烯單位)等。Examples of the arbitrary repeating unit include: a repeating unit having a structure obtained by polymerizing a conjugated diene (conjugated diene unit); a repeating unit having a structure obtained by hydrogenating the aforementioned repeating unit (hydrogenated conjugated diene unit); ene unit) etc.

作為共軛二烯，可舉例如丁二烯、異戊二烯、2,3-二甲基丁二烯、1,3-戊二烯、1,3-己二烯等的脂肪族共軛二烯；氯丁二烯等的鹵化脂肪族共軛二烯等。作為共軛二烯，就可顯著地得到本發明的效果之觀點而言，較佳為脂肪族共軛二烯，又較佳為丁二烯。共軛二烯係可單獨使用1種類、或可組合2種類以上來使用。Examples of the conjugated diene include aliphatic conjugates such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, and 1,3-hexadiene. Dienes; halogenated aliphatic conjugated dienes such as chloroprene, etc. As the conjugated diene, from the viewpoint that the effects of the present invention can be significantly obtained, an aliphatic conjugated diene is preferred, and butadiene is more preferred. One type of conjugated diene may be used alone, or two or more types may be used in combination.

(C)苯乙烯系彈性體亦可為無規共聚物，但就可顯著地得到本發明的效果之觀點而言，較佳為嵌段共聚物。作為(C)苯乙烯系彈性體，較佳為苯乙烯-共軛二烯嵌段共聚物、氫化苯乙烯-共軛二烯共聚物。作為特佳的(C)苯乙烯系彈性體可舉例如下述之嵌段共聚物：具有包含苯乙烯單位的聚合嵌段來作為至少1個的末端嵌段，且具有包含共軛二烯單位或氫化共軛二烯單位的聚合嵌段來作為至少1個的中間嵌段而成的嵌段共聚物。(C) The styrenic elastomer may be a random copolymer, but from the viewpoint that the effects of the present invention can be significantly obtained, a block copolymer is preferred. As (C) the styrene-based elastomer, a styrene-conjugated diene block copolymer and a hydrogenated styrene-conjugated diene copolymer are preferred. An example of a particularly preferred (C) styrenic elastomer is a block copolymer having a polymerized block containing a styrene unit as at least one terminal block and having a conjugated diene unit or A block copolymer in which at least one middle block is formed by hydrogenating a polymerized block of conjugated diene units.

所謂的氫化苯乙烯-共軛二烯嵌段共聚物，係表示具有將苯乙烯-共軛二烯嵌段共聚物的不飽和鍵氫化而得到的構造的嵌段共聚物。通常而言，該氫化苯乙烯-共軛二烯嵌段共聚物係脂肪族的不飽和鍵會被氫化，而苯環等的芳香族的不飽和鍵未被氫化。The hydrogenated styrene-conjugated diene block copolymer refers to a block copolymer having a structure obtained by hydrogenating the unsaturated bonds of the styrene-conjugated diene block copolymer. Generally speaking, in this hydrogenated styrene-conjugated diene block copolymer, aliphatic unsaturated bonds are hydrogenated, but aromatic unsaturated bonds such as benzene rings are not hydrogenated.

作為(C)苯乙烯系彈性體的具體例，可舉例苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-異戊二烯-苯乙烯嵌段共聚物(SIS)、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)、苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEPS)、苯乙烯-乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEEPS)、苯乙烯-丁二烯-丁烯-苯乙烯嵌段共聚物(SBBS)、苯乙烯-丁二烯二嵌段共聚物、氫化苯乙烯-丁二烯嵌段共聚物、氫化苯乙烯-異戊二烯嵌段共聚物、氫化苯乙烯-丁二烯無規共聚物等。Specific examples of (C) styrene-based elastomer include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), Styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated benzene Ethylene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer, etc.

(C)苯乙烯系彈性體的重量平均分子量(Mw)，就可顯著地得到本發明所期望之效果之觀點而言，較佳為1000～500000，又較佳為2000～300000，更佳為3000～200000。(C)苯乙烯系彈性體的重量平均分子量，可和(A)環氧樹脂的重量平均分子量以相同的方法來進行測定。(C) The weight average molecular weight (Mw) of the styrenic elastomer is preferably 1,000 to 500,000, more preferably 2,000 to 300,000, and even more preferably 1,000 to 500,000, from the viewpoint of significantly obtaining the desired effects of the present invention. 3000～200000. The weight average molecular weight of (C) the styrene-based elastomer can be measured by the same method as the weight average molecular weight of (A) the epoxy resin.

作為(C)苯乙烯系彈性體中的苯乙烯單位的含量，將(C)成分設為100質量%時，較佳為61質量%以上，又較佳為63質量%以上，更佳為65質量%以上。上限方面，較佳為80質量%以下，又較佳為75質量%以下，更佳為70質量%以下。藉由將苯乙烯單位的含量設為上述範圍內，能夠更提高與(A)環氧樹脂及(B)硬化劑的相溶性，可得到高溫高濕環境試驗後的絕緣可靠性為優異的硬化物。又，可使透濕係數調整為較低。前述的苯乙烯單位的含量，例如，可依據構成(C)成分的單體的置入量來進行測定。The content of styrene units in (C) the styrene-based elastomer is preferably 61 mass% or more, more preferably 63 mass% or more, and more preferably 65 mass% when the (C) component is 100 mass%. Quality% or more. The upper limit is preferably 80 mass% or less, more preferably 75 mass% or less, and more preferably 70 mass% or less. By setting the content of styrene units within the above range, the compatibility with (A) epoxy resin and (B) hardener can be further improved, and a hardened resin with excellent insulation reliability after a high-temperature and high-humidity environment test can be obtained. things. In addition, the moisture permeability coefficient can be adjusted to be low. The content of the aforementioned styrene units can be measured, for example, based on the amount of the monomer constituting the component (C).

(C)成分可使用市售品，可舉例如氫化苯乙烯系熱可塑性彈性體「H1041」、「Tuftec H1043」、「Tuftec P2000」、「Tuftec MP10」(旭化成公司製)；環氧化苯乙烯-丁二烯熱可塑性彈性體「Epofriend AT501」、「CT310」(Daicel公司製)；具有羥基的變性苯乙烯系彈性體「Septon HG252」(Kuraray公司製)；具有羧基的變性苯乙烯系彈性體「Tuftec N503M」、具有胺基的變性苯乙烯系彈性體「Tuftec N501」、具有酸酐基的變性苯乙烯系彈性體「Tuftec M1913」(‎Asahi Kasei Chemicals公司製)；未變性苯乙烯系彈性體「Septon S8104」(Kuraray公司製)等。(C)成分係可單獨使用1種類、或可組合2種類以上來使用。Commercially available products can be used as the component (C). Examples include hydrogenated styrenic thermoplastic elastomer "H1041", "Tuftec H1043", "Tuftec P2000", and "Tuftec MP10" (manufactured by Asahi Kasei Co., Ltd.); epoxidized styrene- Butadiene thermoplastic elastomers "Epofriend AT501" and "CT310" (manufactured by Daicel); modified styrenic elastomer having a hydroxyl group "Septon HG252" (manufactured by Kuraray); modified styrenic elastomer having a carboxyl group " Tuftec N503M", modified styrenic elastomer with amine group "Tuftec N501", modified styrenic elastomer with acid anhydride group "Tuftec M1913" (manufactured by Asahi Kasei Chemicals Co., Ltd.); unmodified styrenic elastomer" Septon S8104" (manufactured by Kuraray Co., Ltd.), etc. (C) Component system can be used individually by 1 type, or can be used in combination of 2 or more types.

(C)成分的含量，就可顯著地得到本發明的效果之觀點而言，將樹脂組成物中的不揮發成分設為100質量%時，較佳為0.5質量%以上，又較佳為0.6質量%以上，更佳為0.7質量%以上。上限方面，較佳為18質量%以下，又較佳為15質量%以下，更佳為10質量%以下、4質量%以下。The content of component (C) is preferably 0.5 mass% or more, further preferably 0.6, when the non-volatile component in the resin composition is 100 mass%, so as to significantly obtain the effects of the present invention. mass% or more, more preferably 0.7 mass% or more. The upper limit is preferably 18 mass% or less, more preferably 15 mass% or less, more preferably 10 mass% or less, and 4 mass% or less.

將樹脂組成物中的不揮發成分設為100質量%時的(C)成分的含量定為C1，將樹脂組成物中的不揮發成分設為100質量%時的(B)成分的含量定為B1。此時，就可顯著地得到本發明的效果之觀點而言，C1/B1較佳為0.01以上，又較佳為0.05以上，更佳為0.1以上；較佳為10以下，又較佳為5以下，更佳為3以下。The content of the component (C) when the nonvolatile component in the resin composition is 100 mass % is C1, and the content of the component (B) when the nonvolatile component in the resin composition is 100 mass % is B1. In this case, from the viewpoint that the effect of the present invention can be significantly obtained, C1/B1 is preferably 0.01 or more, more preferably 0.05 or more, more preferably 0.1 or more; preferably 10 or less, and more preferably 5 or less, more preferably 3 or less.

＜(D)具有自由基聚合性不飽和基的樹脂＞ 第一實施形態的樹脂組成物，(D)具有自由基聚合性不飽和基的樹脂之中含有(D-1)具有(甲基)丙烯醯基的樹脂。第二實施形態的樹脂組成物則含有(D)具有自由基聚合性不飽和基的樹脂。<(D) Resin having radically polymerizable unsaturated group> The resin composition of the first embodiment contains (D-1) a resin having a (meth)acrylyl group among the resin having (D) a radically polymerizable unsaturated group. The resin composition of the second embodiment contains (D) a resin having a radically polymerizable unsaturated group.

作為第二實施形態的樹脂組成物的一實施形態，(D)成分為包含(D-1)具有(甲基)丙烯醯基的樹脂的態樣。又，作為其他的一實施形態，係包含(D-1)具有(甲基)丙烯醯基的樹脂及(D-2)具有乙烯基苯基的樹脂的態樣。就可顯著地得到本發明的效果之觀點而言，樹脂組成物較佳為同時包含(D-1)成分及(D-2)成分。As an embodiment of the resin composition of the second embodiment, the component (D) contains (D-1) a resin having a (meth)acryl group. Moreover, as another embodiment, it is the aspect which contains (D-1) the resin which has a (meth)acrylyl group, and (D-2) the resin which has a vinylphenyl group. From the viewpoint that the effects of the present invention can be significantly obtained, the resin composition preferably contains both the component (D-1) and the component (D-2).

所謂的自由基聚合性不飽和基，係指具有乙烯性雙鍵的基，前述乙烯性雙鍵係藉由活性能量線的照射而展現出硬化性者。作為如此般的基，可舉例如乙烯基、乙烯基苯基、丙烯醯基、甲基丙烯醯基、馬來醯亞胺基、反丁烯二醯基(fumaroyl)、順丁烯二醯基(maleoyl)，以選自乙烯基苯基、丙烯醯基及甲基丙烯醯基中的1種為較佳。The radically polymerizable unsaturated group refers to a group having an ethylenic double bond that exhibits curability by irradiation with active energy rays. Examples of such a group include vinyl, vinylphenyl, acrylyl, methacrylyl, maleimide, fumaroyl, and maleyl. (maleoyl), preferably one selected from the group consisting of vinylphenyl, acryloyl and methacryloyl.

-(D-1)具有(甲基)丙烯醯基的樹脂- 樹脂組成物通常為含有(D-1)具有(甲基)丙烯醯基的樹脂。藉由使樹脂組成物中含有(D-1)具有(甲基)丙烯醯基的樹脂，可得到介電正切為低的硬化物。若使用(D-1)具有(甲基)丙烯醯基的樹脂時，通常而言可使該硬化物的介電正切降低，但是(D-1)成分係具有與(A)成分及(B)成分產生相分離之傾向。然而，本發明中係進而藉由組合並含有(C)成分而抑制了相分離，能夠得到高溫高濕環境試驗後的絕緣可靠性為優異、介電正切為低的硬化物。又，藉由抑制相分離，可使透濕係數調整為較低。 在此，所謂的用語「(甲基)丙烯酸」，係包含丙烯酸及甲基丙烯酸以及此等的組合。-(D-1) Resin having (meth)acrylyl group- The resin composition usually contains (D-1) a resin having a (meth)acryl group. By containing (D-1) the resin having a (meth)acrylyl group in the resin composition, a cured product having a low dielectric tangent can be obtained. When (D-1) is used, the resin having a (meth)acrylyl group can generally lower the dielectric tangent of the cured product. However, the component (D-1) has the same properties as the component (A) and (B). ) components tend to phase separate. However, in the present invention, phase separation is suppressed by further combining and containing the component (C), and a cured product with excellent insulation reliability and low dielectric tangent after a high-temperature and high-humidity environment test can be obtained. In addition, by suppressing phase separation, the moisture permeability coefficient can be adjusted to be low. Here, the term "(meth)acrylic acid" includes acrylic acid, methacrylic acid, and combinations thereof.

就得到介電正切為低的硬化物之觀點而言，(D-1)具有(甲基)丙烯醯基的樹脂係較佳為於每1分子中具有2個以上的(甲基)丙烯醯基。 所謂的用語「(甲基)丙烯醯基」，係包含丙烯醯基及甲基丙烯醯基以及此等的組合。From the viewpoint of obtaining a cured product with a low dielectric tangent, the resin system (D-1) having a (meth)acryl group preferably has two or more (meth)acryl groups per molecule. base. The term "(meth)acrylyl group" includes acrylyl group, methacrylyl group and combinations thereof.

就得到介電正切為低的硬化物之觀點而言，(D-1)具有(甲基)丙烯醯基的樹脂較佳為具有環狀構造。作為環狀構造，較佳為2價的環狀基。作為2價的環狀基，可任意為包含脂環式構造的環狀基或包含芳香環構造的環狀基。又，可具有複數個2價的環狀基。From the viewpoint of obtaining a cured product with a low dielectric tangent, the resin having a (meth)acryl group (D-1) preferably has a cyclic structure. As the cyclic structure, a divalent cyclic group is preferred. The divalent cyclic group may be any cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Moreover, it may have a plurality of divalent cyclic groups.

就可顯著地得到本發明所期望之效果之觀點而言，2價的環狀基較佳為3員環以上，又較佳為4員環以上，更佳為5員環以上；較佳為20員環以下，又較佳為15員環以下，更佳為10員環以下。又，作為2價的環狀基，可為單環構造，亦可為多環構造。From the viewpoint of significantly obtaining the desired effects of the present invention, the divalent cyclic group is preferably a ring with 3 members or more, more preferably a ring with 4 members or more, and more preferably a ring with 5 members or more; preferably The number of members is less than 20 members, preferably less than 15 members, and more preferably less than 10 members. In addition, the divalent cyclic group may have a monocyclic structure or a polycyclic structure.

2價的環狀基中的環，除了碳原子以外，亦可藉由雜原子來構成環的骨架。作為雜原子，可舉例如氧原子、硫原子、氮原子等，較佳為氧原子。前述的環中可具有1個雜原子，亦可具有2個以上。In addition to carbon atoms, the ring in the divalent cyclic group may also be composed of heteroatoms to form the skeleton of the ring. Examples of the hetero atom include oxygen atom, sulfur atom, nitrogen atom, etc., and an oxygen atom is preferred. The aforementioned ring may have one heteroatom or two or more heteroatoms.

作為2價的環狀基的具體例，可舉例下述的2價的基(i)～(xi)。其中，作為2價的環狀基較佳為(x)或(xi)。 Specific examples of the divalent cyclic group include the following divalent groups (i) to (xi). Among these, the divalent cyclic group is preferably (x) or (xi).

2價的環狀基亦可具有取代基。作為如此般的取代基，可舉例如鹵素原子、烷基、烷氧基、芳基、芳烷基、矽基、醯基、醯氧基、羧基、磺酸基、氰基、硝基、羥基、巰基、側氧基等，較佳為烷基。The divalent cyclic group may have a substituent. Examples of such substituents include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a silyl group, a hydroxyl group, a hydroxyl group, a carboxyl group, a sulfonic acid group, a cyano group, a nitro group, and a hydroxyl group. , mercapto group, side oxygen group, etc., preferably alkyl group.

(甲基)丙烯醯基可直接鍵結於2價的環狀基，亦可介隔著2價的連結基來進行鍵結。作為2價的連結基，可舉例如伸烷基、伸烯基、伸芳基、伸雜芳基、 -C(=O)O-、-O-、-NHC(=O)-、-NC(=O)N-、-NHC(=O)O-、-C(=O)-、-S-、-SO-、-NH-等，亦可為組合複數個該等而成的基。作為伸烷基，較佳為碳原子數1～10的伸烷基，又較佳為碳原子數1～6的伸烷基，更佳為碳原子數1～5的伸烷基或碳原子數1～4的伸烷基。伸烷基可任意為直鏈、分支或環狀。作為如此般的伸烷基，可舉例如亞甲基、伸乙基、伸丙基、伸丁基、伸戊基、伸己基、1,1-二甲基伸乙基等，較佳為亞甲基、伸乙基、1,1-二甲基伸乙基。作為伸烯基，較佳為碳原子數2～10的伸烯基，又較佳為碳原子數2～6的伸烯基，更佳為碳原子數2～5的伸烯基。作為伸芳基、伸雜芳基，較佳為碳原子數6～20的伸芳基或伸雜芳基，又較佳為碳原子數6～10的伸芳基或伸雜芳基。作為2價的連結基，較佳為伸烷基，其中，較佳為亞甲基、1,1-二甲基伸乙基。The (meth)acrylyl group may be directly bonded to a divalent cyclic group, or may be bonded via a divalent linking group. Examples of the divalent linking group include an alkylene group, an alkenylene group, an aryl group, a heteroaryl group, -C(=O)O-, -O-, -NHC(=O)-, and -NC. (=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc. may also be a combination of a plurality of these groups. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms or a carbon atom. Alkylene group with number 1 to 4. The alkylene group can be optionally linear, branched or cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1,1-dimethylethylene, and the like. Methyl, ethylidene, 1,1-dimethylethylidene. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferred, an alkenylene group having 2 to 6 carbon atoms is more preferred, and an alkenylene group having 2 to 5 carbon atoms is more preferred. As the aryl group or heteroaryl group, an aryl group or heteroaryl group having 6 to 20 carbon atoms is preferred, and an aryl group or heteroaryl group having 6 to 10 carbon atoms is more preferred. As the divalent linking group, an alkylene group is preferred, and among these, a methylene group and a 1,1-dimethylethylene group are preferred.

(D-1)具有(甲基)丙烯醯基的樹脂，較佳為以下述式(1)表示。 (式(1)中，R1 及R4 分別獨立表示(甲基)丙烯醯基，R2 及R3 分別獨立表示2價的連結基，環A表示2價的環狀基)。(D-1) A resin having a (meth)acrylyl group is preferably represented by the following formula (1). (In the formula (1), R 1 and R 4 each independently represent a (meth)acrylyl group, R 2 and R 3 each independently represent a divalent linking group, and ring A represents a divalent cyclic group).

R1 及R4 分別獨立表示丙烯醯基或甲基丙烯醯基，較佳為丙烯醯基。R 1 and R 4 independently represent an acrylic group or a methacrylic group, preferably an acrylic group.

R2 及R3 分別獨立表示2價的連結基。作為2價的連結基，係與上述的2價的連結基為相同。R 2 and R 3 each independently represent a divalent linking group. The divalent coupling group is the same as the above-mentioned divalent coupling group.

環A表示2價的環狀基。作為環A，係與上述的2價的環狀基為相同。Ring A represents a divalent cyclic group. Ring A is the same as the above-mentioned divalent cyclic group.

環A亦可具有取代基。作為取代基，係與上述的2價的環狀基可具有的取代基為相同。Ring A may have a substituent. The substituent is the same as the substituent that the above-mentioned divalent cyclic group may have.

以下為表示(D-1)成分的具體例，但本發明並不被限定於此。 The following are specific examples of the component (D-1), but the present invention is not limited thereto.

(D-1)成分可使用市售品，可舉例如新中村化學工業公司製的「A-DOG」、共榮社化學公司製的「DCP-A」等。(D-1)成分係可單獨使用1種類、或可組合2種類以上來使用。(D-1) Commercially available products can be used as the component, and examples thereof include "A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., "DCP-A" manufactured by Kyoeisha Chemical Co., Ltd., and the like. (D-1) Component system can be used individually by 1 type, or can be used in combination of 2 or more types.

(D-1)成分的分子量，就可顯著地得到本發明所期望之效果之觀點而言，較佳為2000以下，又較佳為1000以下，更佳為500以下。下限方面，較佳為100以上，又較佳為200以上，更佳為300以上。The molecular weight of component (D-1) is preferably 2,000 or less, more preferably 1,000 or less, and more preferably 500 or less from the viewpoint of significantly obtaining the desired effects of the present invention. The lower limit is preferably 100 or more, more preferably 200 or more, and more preferably 300 or more.

(D-1)成分的數平均分子量，就可顯著地得到本發明所期望之效果之觀點而言，較佳為3000以下，又較佳為2500以下，更佳為2000以下、1500以下。下限方面，較佳為100以上，又較佳為300以上，更佳為500以上、1000以上。數平均分子量係使用凝膠滲透層析(GPC)所測得的聚苯乙烯換算的數平均分子量。The number average molecular weight of the component (D-1) is preferably 3,000 or less, more preferably 2,500 or less, and more preferably 2,000 or less and 1,500 or less from the viewpoint of significantly obtaining the desired effects of the present invention. As for the lower limit, 100 or more is preferred, 300 or more is more preferred, and 500 or more and 1,000 or more are more preferred. The number average molecular weight is a polystyrene-converted number average molecular weight measured using gel permeation chromatography (GPC).

(D-1)成分的含量，就可顯著地得到本發明的效果之觀點而言，將樹脂組成物中的不揮發成分設為100質量%時，較佳為5質量%以上，又較佳為10質量%以上，更佳為15質量%以上。上限方面，較佳為50質量%以下，又較佳為40質量%以下，更佳為30質量%以下。From the viewpoint of significantly obtaining the effects of the present invention, the content of component (D-1) is preferably 5 mass% or more when the non-volatile component in the resin composition is 100 mass%, and more preferably It is 10 mass % or more, more preferably, it is 15 mass % or more. The upper limit is preferably 50 mass% or less, more preferably 40 mass% or less, and more preferably 30 mass% or less.

-(D-2)具有乙烯基苯基的樹脂- 除了(D-1)成分以外，樹脂組成物較佳為進一步含有(D-2)具有乙烯基苯基的樹脂。所謂的乙烯基苯基，係具有下述所示之構造的基。 (＊表示鍵結鍵)。-(D-2) Resin having a vinylphenyl group- In addition to the component (D-1), the resin composition preferably further contains (D-2) a resin having a vinylphenyl group. The vinylphenyl group is a group having the structure shown below. (* indicates bonded bond).

(D-2)具有乙烯基苯基的樹脂，就得到介電正切為低的硬化物之觀點而言，較佳為於每1分子中具有2個以上的乙烯基苯基。(D-2) The resin having a vinylphenyl group preferably has two or more vinylphenyl groups per molecule from the viewpoint of obtaining a cured product with a low dielectric tangent.

(D-2)具有乙烯基苯基的樹脂，就得到介電正切為低的硬化物之觀點而言，較佳為具有環狀構造。作為環狀構造，較佳為2價的環狀基。作為2價的環狀基，可任意為包含脂環式構造的環狀基或包含芳香環構造的環狀基。又，可具有複數個2價的環狀基。(D-2) The resin having a vinylphenyl group preferably has a cyclic structure from the viewpoint of obtaining a cured product with a low dielectric tangent. As the cyclic structure, a divalent cyclic group is preferred. The divalent cyclic group may be any cyclic group containing an alicyclic structure or a cyclic group containing an aromatic ring structure. Moreover, it may have a plurality of divalent cyclic groups.

就可顯著地得到本發明所期望之效果之觀點而言，2價的環狀基較佳為3員環以上，又較佳為4員環以上，更佳為5員環以上；較佳為20員環以下，又較佳為15員環以下，更佳為10員環以下。又，作為2價的環狀基，可為單環構造，亦可為多環構造。From the viewpoint of significantly obtaining the desired effects of the present invention, the divalent cyclic group is preferably a ring with 3 members or more, more preferably a ring with 4 members or more, and more preferably a ring with 5 members or more; preferably The number of members is less than 20 members, preferably less than 15 members, and more preferably less than 10 members. In addition, the divalent cyclic group may have a monocyclic structure or a polycyclic structure.

2價的環狀基中的環，除了碳原子以外，亦可藉由雜原子來構成環的骨架。作為雜原子，可舉例如氧原子、硫原子、氮原子等，較佳為氧原子。前述的環中可具有1個雜原子，亦可具有2個以上。In addition to carbon atoms, the ring in the divalent cyclic group may also be composed of heteroatoms to form the skeleton of the ring. Examples of the hetero atom include oxygen atom, sulfur atom, nitrogen atom, etc., and an oxygen atom is preferred. The aforementioned ring may have one heteroatom or two or more heteroatoms.

作為2價的環狀基的具體例，可舉例下述的2價的基(xii)或(xiii)。 (2價的基(xii)、(xiii)中，R1 、R2 、R5 、R6 、R7 、R11 及R12 分別獨立表示鹵素原子、碳原子數6以下的烷基或苯基，R3 、R4 、R8 、R9 及R10 分別獨立表示氫原子、鹵素原子、碳原子數6以下的烷基或苯基)。Specific examples of the divalent cyclic group include the following divalent group (xii) or (xiii). (In the divalent groups (xii) and (xiii), R 1 , R 2 , R 5 , R 6 , R 7 , R 11 and R 12 each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms or benzene. group, R 3 , R 4 , R 8 , R 9 and R 10 each independently represent a hydrogen atom, a halogen atom, an alkyl group with 6 or less carbon atoms or a phenyl group).

作為鹵素原子，可舉例氟原子、氯原子、溴原子、碘原子。作為碳原子數6以下的烷基，可舉例甲基、乙基、丙基、丁基、戊基、己基等，較佳為甲基。作為R1 、R2 、R5 、R6 、R7 、R11 及R12 ，較佳以甲基來表示。R3 、R4 、R8 、R9 及R10 ，較佳為氫原子或甲基。Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 6 or less carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, etc., with methyl being preferred. R 1 , R 2 , R 5 , R 6 , R 7 , R 11 and R 12 are preferably represented by a methyl group. R 3 , R 4 , R 8 , R 9 and R 10 are preferably hydrogen atoms or methyl groups.

又，2價的環狀基亦可為組合複數個2價的環狀基。作為組合2價的環狀基的具體例，可舉例以下述的式(a)表示的2價的環狀基(2價的基(a))。 (式(a)中，R21 、R22 、R25 、R26 、R27 、R31 、R32 、R35 及R36 分別獨立表示鹵素原子、碳原子數6以下的烷基或苯基，R23 、R24 、R28 、R29 、R30 、R33 及R34 分別獨立表示氫原子、鹵素原子、碳原子數6以下的烷基或苯基，n及m為表示0～300的整數，但不包括n及m之一方為0之情形)。Furthermore, the divalent cyclic group may be a combination of a plurality of divalent cyclic groups. Specific examples of combinations of bivalent cyclic groups include a bivalent cyclic group (bivalent group (a)) represented by the following formula (a). (In formula (a), R 21 , R 22 , R 25 , R 26 , R 27 , R 31 , R 32 , R 35 and R 36 each independently represent a halogen atom, an alkyl group with 6 or less carbon atoms or a phenyl group. , R 23 , R 24 , R 28 , R 29 , R 30 , R 33 and R 34 independently represent a hydrogen atom, a halogen atom, an alkyl group with less than 6 carbon atoms or a phenyl group, n and m represent 0 to 300 an integer, but excluding the case where one of n and m is 0).

R21 、R22 、R35 及R36 ，係與2價的基(xii)中的R1 為相同。R23 、R24 、R33 及R34 ，係與2價的基(xii)中的R3 為相同。R25 、R26 、R27 、R31 及R32 ，係與式(xiii)中的R5 為相同。R28 、R29 及R30 ，係與式(xiii)中的R8 為相同。R 21 , R 22 , R 35 and R 36 are the same as R 1 in the divalent group (xii). R 23 , R 24 , R 33 and R 34 are the same as R 3 in the divalent group (xii). R 25 , R 26 , R 27 , R 31 and R 32 are the same as R 5 in formula (xiii). R 28 , R 29 and R 30 are the same as R 8 in formula (xiii).

n及m為表示0～300的整數。但不包括n及m之一方為0之情形。作為n及m，較佳為表示1～100的整數，又較佳為表示1～50的整數，更較佳為表示1～10的整數。n及m可為相同或相異。n and m are integers representing 0 to 300. But it does not include the case where one of n and m is 0. As n and m, an integer representing 1 to 100 is preferred, an integer representing 1 to 50 is more preferred, and an integer representing 1 to 10 is more preferred. n and m can be the same or different.

2價的環狀基亦可具有取代基。作為取代基，係與(D-1)成分中的2價的環狀基可具有的取代基為相同。The divalent cyclic group may have a substituent. The substituent is the same as the substituent that the divalent cyclic group in the component (D-1) may have.

乙烯基苯基可直接鍵結於2價的環狀基，亦可介隔著2價的連結基來進行鍵結。作為2價的連結基，可如同在「-(D-1)具有(甲基)丙烯醯基的樹脂-」的欄位中所說明般。作為2價的連結基，較佳為伸烷基，其中，較佳為亞甲基。The vinylphenyl group may be directly bonded to a divalent cyclic group, or may be bonded via a divalent linking group. As a divalent coupling group, it can be as described in the column of "-(D-1) Resin having a (meth)acrylyl group-". As the divalent linking group, an alkylene group is preferred, and among these, a methylene group is preferred.

(D-2)具有乙烯基苯基的樹脂，較佳為以下述式(2)表示。 (式(2)中，R41 及R42 分別獨立表示2價的連結基，環B表示2價的環狀基)。(D-2) A resin having a vinylphenyl group is preferably represented by the following formula (2). (In the formula (2), R 41 and R 42 each independently represent a divalent linking group, and ring B represents a divalent cyclic group).

R41 及R42 分別獨立表示2價的連結基。作為2價的連結基，係與上述的2價的連結基為相同。R 41 and R 42 each independently represent a divalent linking group. The divalent coupling group is the same as the above-mentioned divalent coupling group.

環B表示2價的環狀基。作為環B，係與上述的2價的環狀基為相同。Ring B represents a divalent cyclic group. Ring B is the same as the above-mentioned divalent cyclic group.

環B亦可具有取代基。作為取代基，係與上述的2價的環狀基可具有的取代基為相同。Ring B may have a substituent. The substituent is the same as the substituent that the above-mentioned divalent cyclic group may have.

以下為表示(D-2)成分的具體例，但本發明並不限定於此。 (n1係與式(a)中的n為相同，m1係與式(a)中的m為相同)。The following are specific examples of the component (D-2), but the present invention is not limited thereto. (n1 is the same as n in the formula (a), and m1 is the same as m in the formula (a)).

(D-2)成分可使用市售品，可舉例如Mitsubishi Gas Chemical公司製的「OPE-2St」等。(D-2)成分係可單獨使用1種類、或可組合2種類以上來使用。(D-2) A commercially available product can be used as a component, for example, "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd. etc. can be used. (D-2) Component system can be used individually by 1 type, or can be used in combination of 2 or more types.

(D-2)成分的數平均分子量，就可顯著地得到本發明所期望之效果之觀點而言，較佳為3000以下，又較佳為2500以下，更佳為2000以下、1500以下。下限方面，較佳為100以上，又較佳為300以上，更佳為500以上、1000以上。數平均分子量係可與(D-1)成分以相同的方法來進行測定。The number average molecular weight of the component (D-2) is preferably 3,000 or less, more preferably 2,500 or less, and more preferably 2,000 or less and 1,500 or less from the viewpoint of significantly obtaining the desired effects of the present invention. As for the lower limit, 100 or more is preferred, 300 or more is more preferred, and 500 or more and 1,000 or more are more preferred. The number average molecular weight can be measured by the same method as (D-1) component.

(D-2)成分的含量，就可顯著地得到本發明的效果之觀點而言，將樹脂組成物中的不揮發成分設為100質量%時，較佳為5質量%以上，又較佳為10質量%以上，更佳為15質量%以上。上限方面，較佳為50質量%以下，又較佳為40質量%以下，更佳為30質量%以下。From the viewpoint of significantly obtaining the effects of the present invention, the content of component (D-2) is preferably 5 mass% or more, and more preferably 100 mass% of non-volatile components in the resin composition. It is 10 mass % or more, more preferably, it is 15 mass % or more. The upper limit is preferably 50 mass% or less, more preferably 40 mass% or less, and more preferably 30 mass% or less.

樹脂組成物較佳為同時包含(D-1)成分及(D-2)成分。此時，將樹脂組成物中的不揮發成分設為100質量%時的(D-1)成分的含量定為D1，將樹脂組成物中的不揮發成分設為100質量%時的(D-2)成分的含量定為D2之情形時，D2/D1較佳為0.1以上，又較佳為0.3以上，更佳為0.5以上。上限方面，較佳為10以下，又較佳為5以下，更佳為3以下。藉由將D2/D1設為上述範圍內，可得到高溫高濕環境試驗後的絕緣可靠性為優異的硬化物。又，可使透濕係數調整為較低。The resin composition preferably contains both the (D-1) component and the (D-2) component. At this time, the content of the component (D-1) when the nonvolatile component in the resin composition is taken to be 100 mass% is D1, and the content of the component (D-1) when the nonvolatile component in the resin composition is taken to be 100 mass% is (D- 2) When the content of the component is D2, D2/D1 is preferably 0.1 or more, more preferably 0.3 or more, and more preferably 0.5 or more. The upper limit is preferably 10 or less, more preferably 5 or less, and more preferably 3 or less. By setting D2/D1 within the above range, a cured product having excellent insulation reliability after a high-temperature and high-humidity environment test can be obtained. In addition, the moisture permeability coefficient can be adjusted to be low.

＜(E)無機填充材＞ 除了上述成分以外，樹脂組成物亦可進一步含有(E)無機填充材來作為任意的成分。＜(E) Inorganic filler＞ In addition to the above-mentioned components, the resin composition may further contain (E) an inorganic filler as an optional component.

作為無機填充材的材料為使用無機化合物。作為無機填充材的材料的例子，可舉例二氧化矽、氧化鋁、玻璃、堇青石、矽氧化物、硫酸鋇、碳酸鋇、滑石、黏土、雲母粉、氧化鋅、水滑石、水鋁礦、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、氮化鋁、氮化錳、硼酸鋁、碳酸鍶、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、氧化鋯、鈦酸鋇、鈦酸鋯酸鋇、鋯酸鋇、鋯酸鈣、磷酸鋯及鎢磷酸鋯等。該等之中，以二氧化矽為特別適合。作為二氧化矽，可舉例如無定形二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二氧化矽、中空二氧化矽等。又，作為二氧化矽係以球狀二氧化矽為較佳。(E)無機填充材係可單獨使用1種類、或可組合2種類以上來使用。As the inorganic filler material, an inorganic compound is used. Examples of materials for the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and gibbsite. Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate , titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungsten phosphate, etc. Among these, silicon dioxide is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. In addition, as the silica system, spherical silica is preferred. (E) Inorganic filler system can be used individually by 1 type, or can be used in combination of 2 or more types.

作為(E)無機填充材的市售品，可舉例如 Denca公司製的「UFP-30」；Nippon Steel & Sumikin Materials公司製的「SP60-05」、「SP507-05」； Admatechs公司製的「YC100C」、「YA050C」、「 YA050C-MJE」、「YA010C」；Tokuyama公司製的「 Shirufiru NSS-3N」、「Shirufiru NSS-4N」、「Shirufiru NSS-5N」；Admatechs公司製的「SC2500SQ」、「SO-C4」、「SO-C2」、「SO-C1」等。Examples of commercially available products of (E) inorganic filler include: "UFP-30" made by Denca; Nippon Steel & Sumikin "SP60-05" and "SP507-05" made by Materials; "YC100C", "YA050C", " YA050C-MJE", "YA010C"; manufactured by Tokuyama Corporation Shirufiru NSS-3N", "Shirufiru NSS-4N", "Shirufiru NSS-5N"; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" made by Admatechs, etc.

(E)無機填充材的平均粒徑，就可顯著地得到本發明所期望之效果之觀點而言，較佳為0.01μm以上，又較佳為0.05μm以上，特佳為0.1μm以上；較佳為5μm以下，又較佳為2μm以下，更佳為1μm以下。(E) The average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more, in order to significantly obtain the desired effects of the present invention. It is preferably 5 μm or less, more preferably 2 μm or less, and more preferably 1 μm or less.

(E)無機填充材的平均粒徑係可藉由基於米氏(Mie)散射理論之雷射繞射･散射法來進行測定。具體而言係藉由以下之方式來進行測定：藉由雷射繞射散射式粒徑分布測定裝置，以體積基準來製作無機填充材的粒徑分布，並藉由將該均粒徑(median diameter)作為平均粒徑。測定樣品係可使用秤取無機填充材100mg、甲基乙基酮10g至管形瓶中，藉以超音波使其分散10分鐘者。將測定樣品使用雷射繞射式粒徑分布測定裝置，以藍色及紅色設為使用光源波長，利用流通槽方式來測定(E)無機填充材的體積基準的粒徑分布，可從所得到的粒徑分布算出平均粒徑來作為均粒徑。作為雷射繞射式粒徑分布測定裝置，可舉例如堀場製作所公司製「LA-960」等。(E) The average particle size of the inorganic filler can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, the measurement is performed in the following manner: using a laser diffraction and scattering particle size distribution measuring device, the particle size distribution of the inorganic filler is measured on a volume basis, and the average particle size (median particle size) is calculated. diameter) as the average particle diameter. To measure the sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed using ultrasonic waves for 10 minutes. Using a laser diffraction particle size distribution measuring device on the measurement sample, blue and red are used as the light source wavelengths, and the volume-based particle size distribution of (E) the inorganic filler is measured using the flow cell method. From the obtained The average particle size was calculated from the particle size distribution and used as the average particle size. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

(E)無機填充材的比表面積，就可顯著地得到本發明所期望之效果之觀點而言，較佳為1m2 /g以上，又較佳為2m2 /g以上，特佳為3m2 /g以上。上限並無特別限制，但較佳為60m2 /g以下、50m2 /g以下或40m2 /g以下。比表面積為依據BET法，利用比表面積測定裝置(Mountech公司製Macsorb HM-1210)來將氮氣吸附於試料表面，使用BET多點法來算出並得到比表面積。(E) The specific surface area of the inorganic filler is preferably 1 m 2 /g or more, more preferably 2 m 2 /g or more, and particularly preferably 3 m 2 from the viewpoint of significantly obtaining the desired effects of the present invention. /g or above. The upper limit is not particularly limited, but is preferably 60 m 2 /g or less, 50 m 2 /g or less, or 40 m 2 /g or less. The specific surface area is based on the BET method. Nitrogen gas is adsorbed on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Corporation), and the specific surface area is calculated using the BET multi-point method.

(E)無機填充材，就提高耐濕性及分散性之觀點而言，以經表面處理劑進行處理為較佳。作為表面處理劑，可舉例如含有氟的矽烷偶合劑、胺基矽烷系偶合劑、環氧基矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、烷氧基矽烷、有機矽氮烷化合物、鈦酸酯系偶合劑等。又，表面處理劑係可使用單獨1種類、亦可任意地組合2種類以上來使用。(E) Inorganic fillers are preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane, and organosilazane. compounds, titanate coupling agents, etc. Moreover, the surface treatment agent can be used individually by 1 type, and can also be used in combination of 2 or more types arbitrarily.

作為表面處理劑的市售品，可舉例如信越化學工業公司製「KBM403」(3-縮水甘油氧基丙基三甲氧基矽烷)、信越化學工業公司製「KBM803」(3-巰基丙基三甲氧基矽烷)、信越化學工業公司製「KBE903」(3-胺基丙基三乙氧基矽烷)、信越化學工業公司製「KBM573」(N-苯基-3-胺基丙基三甲氧基矽烷)、信越化學工業公司製「SZ-31」(六甲基二矽氮烷)、信越化學工業公司製「KBM103」(苯基三甲氧基矽烷)、信越化學工業公司製「KBM-4803」(長鏈環氧基型矽烷偶合劑)、信越化學工業公司製「KBM-7103」(3,3,3-三氟丙基三甲氧基矽烷)等。Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. and "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. Oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd. Silane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industries, Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Industries, Ltd. (Long-chain epoxy silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., etc.

藉由表面處理劑之表面處理的程度，就無機填充材的分散性提升之觀點而言，以限制在指定的範圍內為較佳。具體而言係無機填充材100質量份，以經0.2質量份～5質量份的表面處理劑來進行表面處理為較佳，以經0.2質量份～3質量份來進行表面處理為較佳，以經0.3質量份～2質量份來進行表面處理為較佳。From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably limited to a specified range. Specifically, 100 parts by mass of the inorganic filler is preferably surface treated with 0.2 to 5 parts by mass of a surface treatment agent, and preferably 0.2 to 3 parts by mass of a surface treatment agent. It is preferable to perform surface treatment with 0.3 parts by mass to 2 parts by mass.

藉由表面處理劑之表面處理的程度係可藉由無機填充材的每單位表面積的碳量來進行評估。無機填充材的每單位表面積的碳量，就無機填充材的分散性提升之觀點而言，以0.02mg/m2 以上為較佳，以0.1mg/m2 以上為又較佳，以0.2mg/m2 以上為更佳。另一方面，就抑制樹脂清漆的熔融黏度及在薄片形態下的熔融黏度的上昇之觀點而言，以1mg/m2 以下為較佳，以0.8mg/m2 以下為又較佳，以0.5mg/m2 以下為更佳。The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and 0.2 mg /m 2 or more is better. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg/m 2 or less is preferred, 0.8 mg/m 2 or less is more preferred, and 0.5 is preferred. mg/m 2 or less is better.

無機填充材的每單位表面積的碳量係可於藉由溶劑(例如甲基乙基酮(MEK))，對表面處理後的無機填充材進行洗淨處理後來進行測定。具體而言，將作為溶劑的充分量的MEK加入至經表面處理劑進行表面處理後的無機填充材中，以25℃超音波洗淨5分鐘。去除上澄液並使固形分乾燥後，使用碳分析計，能夠測定無機填充材的每單位表面積的碳量。作為碳分析計係可使用堀場製作所公司製「EMIA-320V」等。The carbon amount per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning was performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer system, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd., etc. can be used.

(E)無機填充材的含量，就降低介電正切之觀點而言，將樹脂組成物中的不揮發成分設為100質量%時，較佳為50質量%以上，又較佳為51質量%以上，更佳為52質量%以上；較佳為90質量%以下，又較佳為85質量%以下，更佳為80質量%以下。(E) The content of the inorganic filler is preferably 50 mass% or more, and more preferably 51 mass% when the non-volatile component in the resin composition is 100 mass% from the viewpoint of reducing the dielectric tangent. More preferably, it is 52 mass % or more; 90 mass % or less is more preferred, 85 mass % or less is more preferred, and 80 mass % or less is more preferred.

將樹脂組成物中的不揮發成分設為100質量%時的(E)成分的含量定為E1，將樹脂組成物中的不揮發成分設為100質量%時的(D-2)成分的含量定為D2之情形時，D2+E1較佳為85質量%以下，又較佳為83質量%以下，更佳為80質量%以下。下限方面，較佳為50質量%以上，又較佳為55質量%以上，更佳為60質量%以上。藉由將D2+E1設為上述範圍內，能夠得到透濕係數為更低的硬化物。The content of component (E) when the non-volatile component in the resin composition is 100 mass % is E1, and the content of component (D-2) when the non-volatile component in the resin composition is 100 mass % In the case of D2, D2+E1 is preferably 85 mass% or less, more preferably 83 mass% or less, and more preferably 80 mass% or less. The lower limit is preferably 50 mass% or more, more preferably 55 mass% or more, and more preferably 60 mass% or more. By setting D2+E1 within the above range, a cured product with a lower moisture permeability coefficient can be obtained.

＜(F)硬化促進劑＞ 除了上述成分以外，樹脂組成物亦可進一步包含(F)硬化促進劑來作為任意的成分。＜(F) Hardening accelerator＞ In addition to the above-mentioned components, the resin composition may further contain (F) a hardening accelerator as an optional component.

作為硬化促進劑，可舉例如磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、胍系硬化促進劑、金屬系硬化促進劑等。其中，較佳為磷系硬化促進劑、胺系硬化促進劑、咪唑系硬化促進劑、金屬系硬化促進劑，又較佳為胺系硬化促進劑、咪唑系硬化促進劑、金屬系硬化促進劑。硬化促進劑係可單獨使用1種類、或可組合2種類以上來使用。Examples of the hardening accelerator include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and metal-based hardening accelerators. Among them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferred, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are further preferred. . One type of hardening accelerator may be used alone, or two or more types may be used in combination.

作為磷系硬化促進劑，可舉例如三苯基膦、硼酸鏻化合物、四苯基鏻四苯基硼酸鹽、n-丁基鏻四苯基硼酸鹽、四丁基鏻癸酸鹽、(4-甲基苯基)三苯基鏻硫氰酸鹽、四苯基鏻硫氰酸鹽、丁基三苯基鏻硫氰酸鹽等，較佳為三苯基膦、四丁基鏻癸酸鹽。Examples of the phosphorus-based hardening accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4 -Methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine and tetrabutylphosphonium decanoic acid salt.

作為胺系硬化促進劑，可舉例如三乙基胺、三丁基胺等的三烷基胺、4-二甲基胺基砒啶、苄基二甲基胺、2,4,6,-參(二甲基胺基甲基)苯酚、1,8-二吖雙環(5,4,0)-十一烯等，較佳為4-二甲基胺基砒啶、1,8-二吖雙環(5,4,0)-十一烯。Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4,6- (Dimethylaminomethyl)phenol, 1,8-diazinebicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-dimethylaminopyridine, etc. Acridinebicyclo(5,4,0)-undecene.

作為咪唑系硬化促進劑，可舉例如2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-十一烷基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-苯基咪唑、1-氰乙基-2-十一烷基咪唑偏苯三甲酸酯、1-氰乙基-2-苯基咪唑偏苯三甲酸酯、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-十一烷基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪異氰脲酸加成物、2-苯基咪唑異氰脲酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑、2,3-二氫-1H-吡咯[1,2-a]苯并咪唑、1-十二烷基-2-甲基-3-苄基咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉等的咪唑化合物及咪唑化合物與環氧樹脂的加成物，較佳為2-乙基-4-甲基咪唑、1-苄基-2-苯基咪唑。Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-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-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate Ester, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-deca Monoalkyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')] -Ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2 -Phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro -1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. The imidazole compound and the adduct of the imidazole compound and the epoxy resin are preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

作為咪唑系硬化促進劑可使用市售品，可舉例如三菱化學公司製的「P200-H50」等。As the imidazole-based hardening accelerator, commercially available products can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

作為胍系硬化促進劑，可舉例如二氰二胺、1-甲基胍、1-乙基胍、1-環己基胍、1-苯基胍、1-(o-甲苯基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三吖雙環[4.4.0]癸-5-烯、7-甲基-1,5,7-三吖雙環[4.4.0]癸-5-烯、1-甲基雙胍、1-乙基雙胍、1-n-丁基雙胍、1-n-十八烷基雙胍、1,1-二甲基雙胍、1,1-二乙基雙胍、1-環己基雙胍、1-烯丙基雙胍、1-苯基雙胍、1-(o-甲苯基)雙胍等，較佳為二氰二胺、1,5,7-三吖雙環[4.4.0]癸-5-烯。Examples of the guanidine-based hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dicyanodiamine. Methylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1 ,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1 , 1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc., preferably Dicyanodiamide, 1,5,7-triazinebicyclo[4.4.0]dec-5-ene.

作為金屬系硬化促進劑，可舉例如鈷、銅、鋅、鐵、鎳、錳、錫等的金屬之有機金屬錯合物或有機金屬鹽。作為有機金屬錯合物的具體例，可舉出乙醯基丙酮酸鈷(II)、乙醯基丙酮酸鈷(III)等的有機鈷錯合物、乙醯基丙酮酸銅(II)等的有機銅錯合物、乙醯基丙酮酸鋅(II)等的有機鋅錯合物、乙醯基丙酮酸鐵(III)等的有機鐵錯合物、乙醯基丙酮酸鎳(II)等的有機鎳錯合物、乙醯基丙酮酸錳(II)等的有機錳錯合物等。作為有機金屬鹽，可舉出例如辛酸鋅、辛酸錫、環烷酸鋅、環烷酸鈷、硬脂酸錫、硬脂酸鋅等。Examples of metal-based hardening accelerators include organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal complex include organic cobalt complexes such as cobalt (II) acetylpyruvate and cobalt (III) acetylpyruvate, and copper (II) acetylpyruvate. Organic copper complexes, organic zinc complexes such as zinc (II) acetylpyruvate, organic iron complexes such as iron (III) acetylpyruvate, nickel (II) acetylpyruvate Organic nickel complexes such as manganese acetylpyruvate (II) and other organic manganese complexes. Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

(F)硬化促進劑的含量，就可顯著地得到本發明所期望之效果之觀點而言，將樹脂組成物中的不揮發成分設為100質量%時，較佳為0.01質量%以上，又較佳為0.03質量%以上，更佳為0.05質量%以上；較佳為0.3質量%以下，又較佳為0.2質量%以下，更佳為0.1質量%以下。(F) The content of the hardening accelerator is preferably 0.01 mass% or more when the non-volatile components in the resin composition are 100 mass%, so as to significantly obtain the desired effects of the present invention. It is preferably 0.03 mass% or more, more preferably 0.05 mass% or more; it is preferably 0.3 mass% or less, more preferably 0.2 mass% or less, and more preferably 0.1 mass% or less.

＜(G)聚合起始劑＞ 除了上述成分以外，樹脂組成物亦可進一步包含(G)聚合起始劑來作為任意的成分。通常而言，(G)聚合起始劑為具有促進(D)成分中的自由基聚合性不飽和基的交聯之機能。(G)聚合起始劑係可單獨使用1種類、或可合併2種類以上來使用。＜(G) Polymerization initiator＞ In addition to the above-mentioned components, the resin composition may further contain (G) a polymerization initiator as an optional component. Generally speaking, (G) polymerization initiator has the function of promoting crosslinking of the radically polymerizable unsaturated group in (D) component. (G) The polymerization initiator may be used alone or in combination of two or more types.

作為(G)聚合起始劑，可舉例如t-丁基異苯丙基過氧化物、t-丁基過氧基乙酸酯、α,α’-二(t-丁基過氧基)二異丙基苯、t-丁基過氧基月桂酸酯、t-丁基過氧基-2-乙基己酸酯、t-丁基過氧基新癸酸酯、t-丁基過氧基苯甲酸酯等的過氧化物。Examples of the (G) polymerization initiator include t-butylisopropyl peroxide, t-butylperoxyacetate, and α,α'-di(t-butylperoxy). Diisopropylbenzene, t-butylperoxylaurate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneodecanoate, t-butylperoxynedecanoate Peroxides such as oxybenzoates.

作為(G)聚合起始劑的市售品，可舉例如日油公司製的「Perbutyl C」、「Perbutyl A」、「Perbutyl P」、「Perbutyl L」、「Perbutyl O」、「Perbutyl ND」、「Perbutyl Z」、「Percumyl P」、「Percumyl D」等。Examples of commercially available polymerization initiators (G) include "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", and "Perbutyl ND" manufactured by NOF Corporation , "Perbutyl Z", "Percumyl P", "Percumyl D", etc.

(G)聚合起始劑的含量，就可顯著地得到本發明所期望之效果之觀點而言，將樹脂組成物中的不揮發成分設為100質量%時，較佳為0.01質量%以上，又較佳為0.05質量%以上，更佳為0.1質量%以上；較佳為1質量%以下，又較佳為0.5質量%以下，更佳為0.4質量%以下。(G) The content of the polymerization initiator is preferably 0.01 mass% or more when the non-volatile component in the resin composition is 100 mass%, so as to significantly obtain the desired effects of the present invention. It is also preferably 0.05 mass % or more, more preferably 0.1 mass % or more; more preferably 1 mass % or less, more preferably 0.5 mass % or less, more preferably 0.4 mass % or less.

＜(H)其他的添加劑＞ 除了上述成分以外，樹脂組成物亦可進一步包含其他的添加劑來作為任意的成分。作為如此般的添加劑，可舉例如：熱可塑性樹脂(但不包括(C)成分及(D)成分)；有機填充材；增黏劑；消泡劑；流平劑；密著性賦予劑等的樹脂添加劑等。該等的添加劑係可單獨使用1種類、或可組合2種類以上來使用。＜(H) Other additives＞ In addition to the above-mentioned components, the resin composition may further contain other additives as optional components. Examples of such additives include thermoplastic resins (but excluding component (C) and component (D)); organic fillers; tackifiers; defoaming agents; leveling agents; adhesion-imparting agents, etc. resin additives, etc. These additives can be used individually by 1 type, or can be used in combination of 2 or more types.

＜透濕係數＞ 第二實施形態的樹脂組成物為組合(A)～(D)成分，將樹脂組成物以200℃、90分鐘熱硬化後而得之硬化物，具有所謂的該硬化物的透濕係數為0g/mm･m2 ･24h以上10g/mm･m2 ･24h以下之特性。就使高溫高濕環境試驗後的絕緣可靠性成為良好之觀點而言，前述的硬化物的透濕係數為10g/mm･m2 ･24h以下，較佳為7g/mm･m2 ･24h以下，又較佳為5g/mm･m2 ･24h以下。下限方面為0g/mm･m2 ･24h以上，較佳為1g/mm･m2 ･24h以上，又較佳為1.3g/mm･m2 ･24h以上，更佳為1.5g/mm･m2 ･24h以上。又，將第一實施形態的樹脂組成物以200℃、90分鐘熱硬化後而得之硬化物，就所謂的該硬化物亦可成為高溫高濕環境試驗後的絕緣可靠性為良好之觀點而言，以具有前述範圍的透濕係數為佳。前述的透濕係數的測定係可依據後述的實施例中所記載之方法來進行測定。<Moisture Permeability Coefficient> The resin composition of the second embodiment is a cured product obtained by combining components (A) to (D). The resin composition is thermally cured at 200° C. for 90 minutes. The cured product has what is called The moisture permeability coefficient is 0g/mm･m 2 ･24h or more and 10g/mm･m 2 ･24h or less. From the viewpoint of improving the insulation reliability after the high-temperature and high-humidity environment test, the moisture permeability coefficient of the aforementioned hardened material is 10g/mm･m 2 ･24h or less, preferably 7g/mm･m 2 ･24h or less , and preferably 5g/mm･ m2 ･24h or less. The lower limit is 0g/mm･m 2 ･24h or more, preferably 1g/mm･m 2 ･24h or more, more preferably 1.3g/mm･m 2 ･24h or more, and more preferably 1.5g/mm･m 2 ･More than 24h. In addition, the cured product obtained by thermally curing the resin composition of the first embodiment at 200°C for 90 minutes can also be a cured product with good insulation reliability after a high-temperature and high-humidity environment test. In other words, it is preferable to have a moisture permeability coefficient in the aforementioned range. The aforementioned water vapor permeability coefficient can be measured according to the method described in the Examples described later.

＜樹脂組成物的物性、用途＞ 將樹脂組成物以200℃、90分鐘熱硬化後而得之硬化物，展現出所謂的介電正切為低之特性。因此，前述的硬化物係可獲得介電正切為低的絕緣層。作為介電正切，較佳為0.005以下，又較佳為0.0045以下、0.004以下。另一方面，介電正切的下限值並未特別限定，但可設為0.0001以上等。前述的介電正切的評估係可依據後述的實施例中所記載之方法來進行測定。＜Physical properties and uses of resin composition＞ The cured product obtained by thermally curing the resin composition at 200° C. for 90 minutes exhibits the so-called low dielectric tangent characteristic. Therefore, the aforementioned hardened material system can obtain an insulating layer with a low dielectric tangent. The dielectric tangent is preferably 0.005 or less, more preferably 0.0045 or less, or 0.004 or less. On the other hand, the lower limit value of the dielectric tangent is not particularly limited, but may be set to 0.0001 or more. The aforementioned evaluation of the dielectric tangent can be measured according to the method described in the Examples to be described later.

將樹脂組成物以130℃、30分鐘，之後以170℃、30分鐘熱硬化而得之硬化物，展現出所謂的即使是在高溫多濕的條件下絕緣可靠性亦為優異之特性。因此，前述的硬化物係可獲得絕緣可靠性為優異的絕緣層。若絕緣層的厚度為10±1μm時，絕緣電阻值較佳為107 Ω以上，又較佳為108 Ω以上，更佳為109 Ω以上、1010 Ω以上。上限方面並未特別限定，但可設為1015 Ω以下等。絕緣電阻值的測定之詳細係可依據後述的實施例中所記載之方法來進行測定。The cured product obtained by thermally curing the resin composition at 130°C for 30 minutes and then at 170°C for 30 minutes exhibits the so-called excellent insulation reliability even under high-temperature and humid conditions. Therefore, the above-mentioned hardened material system can obtain an insulating layer with excellent insulation reliability. If the thickness of the insulating layer is 10±1 μm, the insulation resistance value is preferably 10 7 Ω or more, more preferably 10 8 Ω or more, more preferably 10 9 Ω or more, and 10 10 Ω or more. The upper limit is not particularly limited, but it can be set to 10 15 Ω or less. The details of the measurement of the insulation resistance value can be measured according to the method described in the Examples described later.

將樹脂組成物以130℃、30分鐘，之後以170℃、30分鐘熱硬化而得之硬化物，通常為展現出所謂的與鍍敷導體層之間的密著強度(剝離強度)為優異之特性。因此，前述的硬化物係可獲得與鍍敷導體層的剝離強度為優異的絕緣層。作為剝離強度較佳為0.3kgf/cm以上，又較佳為0.4kgf/cm以上，更佳為0.5kgf/cm以上。另一方面，剝離強度的上限值並未特別限定，但可設為5kgf/cm以下等。前述的剝離強度的評估係可依據後述的實施例中所記載之方法來進行測定。A cured product obtained by thermally curing a resin composition at 130°C for 30 minutes and then at 170°C for 30 minutes generally exhibits excellent adhesion strength (peel strength) to the plated conductor layer. characteristic. Therefore, the above-mentioned hardened material system can obtain an insulating layer having excellent peeling strength from the plated conductor layer. The peel strength is preferably 0.3 kgf/cm or more, more preferably 0.4 kgf/cm or more, and more preferably 0.5 kgf/cm or more. On the other hand, the upper limit of the peel strength is not particularly limited, but may be 5 kgf/cm or less. The aforementioned peel strength can be evaluated according to the method described in the Examples described later.

本發明的樹脂組成物係可降低介電正切之同時，通常可獲得剝離強度為較大的絕緣層。因此，本發明的樹脂組成物係能夠適合使用於作為絕緣用途的樹脂組成物。具體而言，能夠適合使用於作為：用來形成在絕緣層上形成導體層(包含再配線層)之中，用來形成該絕緣層的樹脂組成物(形成導體層的絕緣層形成用樹脂組成物)。The resin composition of the present invention can lower the dielectric tangent and generally obtain an insulating layer with a large peel strength. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation purposes. Specifically, it can be suitably used as a resin composition for forming a conductor layer (including a rewiring layer) on an insulating layer (a resin composition for forming an insulating layer forming a conductor layer) for forming the insulating layer. things).

又，在後述的多層印刷配線板中，能夠適合使用於作為：用來形成多層印刷配線板的絕緣層的樹脂組成物(多層印刷配線板的絕緣層形成用樹脂組成物)、用來形成印刷配線板的層間絕緣層的樹脂組成物(印刷配線板的層間絕緣層形成用樹脂組成物)。其中，可特別適合使用於作為：具有頂部孔徑為45μm以下的通孔的絕緣層形成用的樹脂組成物；又，可特別適合使用於作為：厚度為20μm以下的絕緣層形成用的樹脂組成物。Furthermore, in the multilayer printed wiring board described below, it can be suitably used as a resin composition for forming an insulating layer of a multilayer printed wiring board (a resin composition for forming an insulating layer of a multilayer printed wiring board), or for forming a printed circuit board. Resin composition for interlayer insulating layers of wiring boards (resin composition for forming interlayer insulating layers of printed wiring boards). Among them, it can be particularly suitably used as a resin composition for forming an insulating layer having a through hole with a top hole diameter of 45 μm or less; and it can be particularly suitably used as a resin composition for forming an insulating layer with a thickness of 20 μm or less. .

又，例如，經由下述的(1)～(6)步驟來製造半導體晶片封裝體時，本發明的樹脂組成物亦能夠適合使用於作為：作為用來形成再配線層的絕緣層的再配線形成層用的樹脂組成物(再配線形成層形成用的樹脂組成物)及用來密封半導體晶片的樹脂組成物(半導體晶片密封用的樹脂組成物)。製造半導體晶片封裝體時，亦可進一步於密封層上形成再配線層。 (1)在基材上層合暫固定薄膜之步驟、 (2)將半導體晶片暫時固定至暫固定薄膜上之步驟、 (3)在半導體晶片上形成密封層之步驟、 (4)將基材及暫固定薄膜從半導體晶片上剝離之步驟、 (5)在半導體晶片的基材及暫固定薄膜為已剝離的面上形成作為絕緣層的再配線形成層之步驟及 (6)在再配線形成層上形成作為導體層的再配線層之步驟。Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as an insulating layer for forming a rewiring layer. A resin composition for forming a layer (a resin composition for forming a rewiring forming layer) and a resin composition for sealing a semiconductor wafer (a resin composition for sealing a semiconductor wafer). When manufacturing the semiconductor chip package, a rewiring layer may be further formed on the sealing layer. (1) The steps of laminating the temporary fixing film on the base material, (2) The step of temporarily fixing the semiconductor chip to the temporary fixing film, (3) The steps of forming a sealing layer on the semiconductor wafer, (4) The step of peeling off the base material and the temporary fixing film from the semiconductor wafer, (5) The step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor wafer from which the base material and the temporary fixing film have been peeled off, and (6) A step of forming a rewiring layer as a conductor layer on the rewiring forming layer.

又，本發明的樹脂組成物係可獲得零件埋置性為良好的絕緣層，故若印刷配線板為零件嵌入電路板時亦可適合使用。In addition, the resin composition of the present invention can obtain an insulating layer with good component embedding properties, so it can be suitably used when the printed wiring board is a circuit board in which components are embedded.

[樹脂薄片] 本發明的樹脂薄片包含支撐體、與設置於該支撐體上的以本發明的樹脂組成物所形成的樹脂組成物層。[Resin sheet] The resin sheet of the present invention includes a support body and a resin composition layer formed of the resin composition of the present invention provided on the support body.

樹脂組成物層的厚度，就印刷配線板的薄型化、及該樹脂組成物的硬化物即使是薄膜亦能夠提供絕緣性為優異的硬化物之觀點而言，較佳為30μm以下，又較佳為20μm以下，更佳為15μm以下、10μm以下。樹脂組成物層的厚度的下限並未特別限定，但通常可設為1μm以上、5μm以上等。The thickness of the resin composition layer is preferably 30 μm or less, and more preferably 30 μm or less, from the viewpoint of thinning the printed wiring board and the fact that the cured product of the resin composition can provide a cured product with excellent insulation properties even if it is a film. It is 20 μm or less, more preferably 15 μm or less, or 10 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but it can generally be set to 1 μm or more, 5 μm or more, or the like.

作為支撐體，可舉例如由塑膠材料所成的薄膜、金屬箔、脫模紙，以由塑膠材料所成的薄膜、金屬箔為較佳。Examples of the support include films, metal foils, and release papers made of plastic materials, and films and metal foils made of plastic materials are preferred.

作為支撐體若使用由塑膠材料所成的薄膜之情形時，作為塑膠材料可舉例如聚對苯二甲酸乙二醇酯(以下有時簡稱為「PET」)、聚萘二甲酸乙二醇酯(以下有時簡稱為「PEN」)等的聚酯；聚碳酸酯(以下有時簡稱為「PC」)；聚甲基丙烯酸甲酯(PMMA)等的丙烯酸；環狀聚烯烴；三乙醯基纖維素(TAC)；聚醚硫醚(PES)；聚醚酮；聚醯亞胺等。其中，以聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯為較佳，以廉價的聚對苯二甲酸乙二醇酯為特佳。When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate Polyesters such as (hereinafter sometimes referred to as "PEN"); polycarbonate (hereinafter sometimes referred to as "PC"); acrylics such as polymethylmethacrylate (PMMA); cyclic polyolefins; triacetyl Cellulose (TAC); polyether sulfide (PES); polyether ketone; polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

作為支撐體若使用金屬箔之情形時，作為金屬箔可舉例如銅箔、鋁箔等。其中，較佳為銅箔。作為銅箔，可以使用由銅的單質金屬所成的箔、也可使用由銅與其他的金屬(例如錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)的合金所成的箔。When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, and the like. Among them, copper foil is preferred. As the copper foil, foils made of copper as a single metal or foils made of alloys of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used. .

支撐體係可以對接合於樹脂組成物層的面，施予消光處理、電暈放電處理、靜電抑制處理。The support system can be subjected to matting treatment, corona discharge treatment, and static electricity suppression treatment to the surface bonded to the resin composition layer.

又，作為支撐體，亦可使用在與樹脂組成物層接合的面上具有脫模層的附帶脫模層的支撐體。作為可使用於附帶脫模層的支撐體的脫模層中的脫模劑，可舉例如由醇酸樹脂、聚烯烴樹脂、胺基甲酸酯樹脂及聚矽氧樹脂所成之群組中所選出的1種以上的脫模劑。附帶脫模層的支撐體，可使用市售品，可舉例如具有以醇酸樹脂系脫模劑為主成分的脫模層而成的PET薄膜的LINTEC公司製的「SK-1」、「AL-5」、「AL-7」、Toray公司製的「Lumirror T60」、帝人公司製的「PUREX」、Unitika公司製的「Unipeel」等。Moreover, as a support body, the support body with a release layer which has a release layer on the surface joined to a resin composition layer can also be used. Examples of the release agent that can be used in the release layer of a support with a release layer include alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. One or more selected release agents. As a support with a release layer, commercially available products can be used. Examples include "SK-1" and "SK-1" manufactured by LINTEC Corporation, which are PET films having a release layer containing an alkyd resin release agent as the main component. AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "PUREX", Unitika's "Unipeel", etc.

作為支撐體的厚度並未特別限定，但較佳為5μm～75μm的範圍，又較佳為10μm～60μm的範圍。尚，若使用附帶脫模層的支撐體之情形時，以附帶脫模層的支撐體全體的厚度設為上述範圍為較佳。The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. Furthermore, when using a support with a release layer, it is preferable that the thickness of the entire support with a release layer is within the above range.

在一實施形態中，因應所需，樹脂薄片亦可進一步包含其他的層。作為上述其他的層，可舉例如：在不相接於樹脂組成物層的支撐體的面(即，和支撐體為相反側的面)上係可依據支撐體來設置保護薄膜等。保護薄膜的厚度並未特別限定，例如為1μm～40μm。藉由層合保護薄膜，可抑制對於樹脂組成物層的表面之灰塵等的附著或傷痕。In one embodiment, the resin sheet may further include other layers as required. Examples of the above-mentioned other layers include: a protective film may be provided on the surface of the support that is not in contact with the resin composition layer (that is, the surface opposite to the support) based on the support. The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating a protective film, adhesion of dust or the like or scratches on the surface of the resin composition layer can be suppressed.

樹脂薄片係可藉由例如下述般來製造：將樹脂組成物溶解至有機溶劑中來調製樹脂清漆，使用模塗佈機等將該樹脂清漆塗佈至支撐體上，進而使其進行乾燥而形成樹脂組成物層。The resin sheet can be produced by, for example, dissolving the resin composition in an organic solvent to prepare a resin varnish, applying the resin varnish to a support using a die coater, and drying it. A resin composition layer is formed.

作為有機溶劑，可舉例如：丙酮、甲基乙基酮(MEK)及環己酮等的酮類；乙酸乙酯、乙酸丁酯、溶纖劑乙酸酯、丙二醇單甲基醚乙酸酯及卡必醇乙酸酯等的乙酸酯類；溶纖劑及丁基卡必醇等的卡必醇類；甲苯及二甲苯等的芳香族烴類；二甲基甲醯胺、二甲基乙醯胺(DMAc)及N-甲基吡咯啶酮等的醯胺系溶劑等。有機溶劑係可單獨使用1種類、或可組合2種類以上來使用。Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether acetate. and acetate esters such as carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethyl Acetamide (DMAc) and amide-based solvents such as N-methylpyrrolidone, etc. One type of organic solvent may be used alone, or two or more types may be used in combination.

乾燥係可藉由加熱、噴吹熱風等的周知的方法來實施。乾燥條件並未特別限定，但以樹脂組成物層中的有機溶劑的含量成為10質量%以下，較佳為以成為5質量%以下來進行乾燥。依樹脂清漆中的有機溶劑的沸點而有所不同，例如若使用包含30質量%～60質量%的有機溶劑的樹脂清漆之情形時，藉由以50℃～150℃使其乾燥3分鐘～10分鐘，從而可形成樹脂組成物層。Drying can be carried out by well-known methods such as heating and blowing hot air. Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. It varies depending on the boiling point of the organic solvent in the resin varnish. For example, when using a resin varnish containing 30% to 60% by mass of organic solvent, dry it at 50°C to 150°C for 3 minutes to 10 minutes to form a resin composition layer.

樹脂薄片係能夠捲取成輥狀來進行保存。若樹脂薄片具有保護薄膜之情形時，藉由將保護薄膜剝下從而變成能夠使用的樹脂薄片。The resin sheet can be rolled up into a roll shape and stored. If the resin sheet has a protective film, the protective film can be peeled off to become a usable resin sheet.

[印刷配線板] 本發明的印刷配線板包含由本發明的樹脂組成物的硬化物所形成的絕緣層。[Printed wiring board] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

例如，使用上述的樹脂薄片，藉由包含下述(I)及(II)的步驟之方法，而可製造印刷配線板。 (I) 以樹脂薄片的樹脂組成物層與內層基板接合之方式，在內層基板上進行層合之步驟、 (II) 將樹脂組成物層進行熱硬化來形成絕緣層之步驟。For example, a printed wiring board can be manufactured using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) The step of laminating the inner substrate by bonding the resin composition layer of the resin sheet to the inner substrate, (II) The step of thermally hardening the resin composition layer to form an insulating layer.

步驟(I)中使用的「內層基板」，係指成為印刷配線板的基板的構件，可舉例如玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚苯醚基板等。又，該基板係可以在該一面或兩面具有導體層，且該導體層亦可進行圖型加工。在基板之一面或兩面上形成有導體層(電路)的內層基板，有時稱為「內層電路基板」。又，製造印刷配線板時，進而應形成的絕緣層及/或導體層的中間製造物，亦包含在本發明所謂的「內層基板」之中。印刷配線板若為零件嵌入電路板時，能夠使用嵌入有零件的內層基板。The "inner layer substrate" used in step (I) refers to a member that becomes the substrate of a printed wiring board, and includes, for example, glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermal substrate Hardened polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one or both sides, and the conductor layer may also be patterned. An inner substrate with a conductor layer (circuit) formed on one or both sides of the substrate is sometimes called an "inner circuit substrate". In addition, the intermediate product of the insulating layer and/or the conductor layer that should be formed when manufacturing the printed wiring board is also included in the so-called "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with embedded components, an inner substrate with embedded components can be used.

內層基板與樹脂薄片的層合，可藉由例如從支撐體側將樹脂薄片與內層基板加熱壓黏，而來進行。作為將樹脂薄片與內層基板加熱壓黏之構件(以下亦稱為「加熱壓黏構件」)，可舉例如經加熱的金屬板(SUS鏡板等)或金屬輥(SUS輥)等。尚，為使樹脂薄片充分追隨內層基板的表面凹凸，並非將加熱壓黏構件與樹脂薄片直接壓製，而是以介隔耐熱橡膠等的彈性材來進行壓製為較佳。The inner layer substrate and the resin sheet can be laminated, for example, by heating and pressing the resin sheet and the inner layer substrate from the support side. Examples of the member for heat and pressure bonding the resin sheet and the inner substrate (hereinafter also referred to as "heat and pressure bonding member") include a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). Furthermore, in order to make the resin sheet fully follow the surface irregularities of the inner substrate, it is better not to directly press the heat-pressing member and the resin sheet, but to press them with an elastic material such as heat-resistant rubber interposed.

內層基板與樹脂薄片的層合，可藉由真空層合法來實施。真空層合法中，加熱壓黏溫度係較佳為60℃～160℃，又較佳為80℃～140℃的範圍，加熱壓黏壓力係較佳為0.098MPa～1.77MPa，又較佳為0.29MPa～1.47MPa的範圍，加熱壓黏時間係較佳為20秒鐘～400秒鐘，又較佳為30秒鐘～300秒鐘的範圍。層合係較佳以壓力26.7hPa以下的減壓條件下來實施。The lamination of the inner substrate and the resin sheet can be carried out by vacuum lamination. In the vacuum lamination method, the heating and pressing temperature system is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and pressing pressure system is preferably in the range of 0.098MPa to 1.77MPa, and more preferably 0.29 In the range of MPa to 1.47 MPa, the heating and pressing viscosity time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. The lamination system is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

層合係可藉由市售的真空貼合機來進行。作為市售的真空貼合機，可舉例如名機製作所公司製的真空加壓式貼合機、Nikko･materials公司製的真空貼合機、分批式真空加壓貼合機等。The lamination system can be performed by a commercially available vacuum laminating machine. Examples of commercially available vacuum laminating machines include a vacuum pressure laminating machine manufactured by Meiki Seisakusho Co., Ltd., a vacuum laminating machine manufactured by Nikko Materials Co., Ltd., and a batch type vacuum pressure laminating machine.

於層合後，可藉由在常壓下(大氣壓下)、例如將加熱壓黏構件從支撐體側來進行壓製(press)，從而進行已層合的樹脂薄片的平滑化處理。平滑化處理的壓製條件係可設定與上述層合的加熱壓黏條件為相同的條件。平滑化處理係可藉由市售的貼合機來進行。尚，層合與平滑化處理亦可使用上述市售的真空貼合機來連續地進行。After lamination, the laminated resin sheets can be smoothed by pressing under normal pressure (atmospheric pressure), for example, by heating and pressing the bonding member from the support side. The pressing conditions of the smoothing treatment can be set to the same conditions as the heating and pressing conditions of the above-mentioned lamination. Smoothing treatment can be performed with a commercially available laminating machine. Furthermore, lamination and smoothing processing can also be performed continuously using the above-mentioned commercially available vacuum laminating machine.

可以在步驟(I)與步驟(II)之間來去除支撐體，亦可以在步驟(II)之後來去除支撐體。The support may be removed between step (I) and step (II), or may be removed after step (II).

步驟(II)中，將樹脂組成物層進行熱硬化來形成絕緣層。樹脂組成物層的熱硬化條件並未特別限定，可使用形成印刷配線板的絕緣層時一般所採用的條件。In step (II), the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions of the resin composition layer are not particularly limited, and conditions generally used when forming an insulating layer of a printed wiring board can be used.

例如，樹脂組成物層的熱硬化條件會依據樹脂組成物的種類等而有所差異，硬化溫度較佳為120℃～240℃，又較佳為150℃～220℃，更佳為170℃～210℃。硬化時間較佳為5分鐘～120分鐘，又較佳為10分鐘～100分鐘，更佳可設為15分鐘～100分鐘。For example, the thermal hardening conditions of the resin composition layer vary depending on the type of the resin composition. The curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and more preferably 170°C to 170°C. 210℃. The hardening time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and more preferably 15 minutes to 100 minutes.

在使樹脂組成物層進行熱硬化前，亦可在低於硬化溫度的溫度下對樹脂組成物層進行預加熱。例如在使樹脂組成物層熱硬化之前，可藉以50℃以上未滿120℃(較佳為60℃以上115℃以下，又較佳為70℃以上110℃以下)的溫度，對樹脂組成物層預加熱5分鐘以上(較佳為5分鐘～150分鐘，又較佳為15分鐘～120分鐘，更佳為15分鐘～100分鐘)。Before thermally curing the resin composition layer, the resin composition layer may also be preheated at a temperature lower than the curing temperature. For example, before thermally hardening the resin composition layer, the resin composition layer can be cured at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 115°C or less, and more preferably 70°C or more and 110°C or less). Preheat for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, more preferably 15 minutes to 100 minutes).

由於絕緣層係藉由本發明的樹脂組成物的硬化物來形成，故能夠將絕緣層的厚度設為較薄。作為絕緣層的厚度，較佳為30μm以下，又較佳為20μm以下，更佳為15μm以下、10μm以下。樹脂組成物層的厚度的下限並未特別限定，但通常可設為1μm以上、5μm以上等。Since the insulating layer is formed from the cured product of the resin composition of the present invention, the thickness of the insulating layer can be made thin. The thickness of the insulating layer is preferably 30 μm or less, more preferably 20 μm or less, more preferably 15 μm or less, or 10 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but it can generally be set to 1 μm or more, 5 μm or more, or the like.

於製造印刷配線板時，亦可進而實施：(III)對絕緣層進行開孔之步驟、(IV)將絕緣層進行粗糙化處理之步驟、(V)形成導體層之步驟。該等的步驟(III)至步驟(V)係可根據被用於印刷配線板的製造中之該業者所周知的各種方法來實施。尚，將支撐體於步驟(II)之後來去除時，該支撐體的去除係可在步驟(II)與步驟(III)之間、在步驟(III)與步驟(IV)之間、或在步驟(IV)與步驟(V)之間來實施。又，因應所需重複實施步驟(II)～步驟(V)的絕緣層及導體層的形成，亦可形成多層配線板。When manufacturing a printed wiring board, it is also possible to further implement: (III) a step of opening holes in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer. These steps (III) to steps (V) can be implemented according to various methods well known in the industry and used for manufacturing printed wiring boards. Furthermore, when the support is removed after step (II), the removal of the support can be between step (II) and step (III), between step (III) and step (IV), or between Implemented between step (IV) and step (V). In addition, by repeating the formation of the insulating layer and the conductor layer in steps (II) to (V) as required, a multilayer wiring board can also be formed.

步驟(III)係對絕緣層進行開孔之步驟，藉此在絕緣層上可形成通孔、穿通孔等的孔。步驟(III)係因應絕緣層的形成中使用的樹脂組成物的組成等，可使用例如鑽孔、雷射、等離子等來實施。孔的尺寸或形狀係可因應印刷配線板的設計來做適當決定。Step (III) is a step of opening holes in the insulating layer, whereby holes such as through-holes and through-holes can be formed on the insulating layer. Step (III) can be implemented using, for example, drilling, laser, plasma, etc., depending on the composition of the resin composition used in forming the insulating layer. The size or shape of the hole can be appropriately determined according to the design of the printed wiring board.

由於絕緣層係藉由本發明的樹脂組成物的硬化物來形成，故能夠將頂部孔徑設為較小。作為前述的孔的頂部孔徑較佳為45μm以下，又較佳為40μm以下，又較佳為35μm以下。下限方面，可設為1μm以上等。Since the insulating layer is formed of the cured product of the resin composition of the present invention, the top hole diameter can be made smaller. The top hole diameter of the aforementioned hole is preferably 45 μm or less, more preferably 40 μm or less, and still more preferably 35 μm or less. The lower limit can be set to 1 μm or more.

步驟(IV)係將絕緣層進行粗糙化處理之步驟。一般而言，於該步驟(IV)中亦可進行膠渣的去除。粗糙化處理的程序、條件並未特別限定，可採用於形成印刷配線板的絕緣層時通常所使用的周知的程序、條件。又，可使用乾式或濕式。若藉由濺鍍來進行導體層之形成時，以例如使用電漿的除膠渣處理等的乾式來進行為較佳。特別是，若上述的樹脂組成物於步驟(III)中的開孔為使用UV(紫外線)雷射時，具有可有效地抑制膠渣之傾向，而適合於乾式除膠渣。Step (IV) is a step of roughening the insulating layer. Generally speaking, the slag can also be removed in this step (IV). The procedures and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions generally used when forming an insulating layer of a printed wiring board can be adopted. In addition, dry type or wet type can be used. When the conductor layer is formed by sputtering, it is preferably carried out by a dry method such as desmearing using plasma. In particular, if UV (ultraviolet) laser is used to open the holes in the above-mentioned resin composition in step (III), it has a tendency to effectively suppress smear and is suitable for dry smear removal.

作為在濺鍍中所使用的氣體，可舉例如氬、氧、CF4 等。該等可使用單獨1種，亦可組合2種以上來使用。Examples of the gas used for sputtering include argon, oxygen, CF4 , and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

在一實施形態中，粗糙化處理後的絕緣層表面的算術平均粗糙度(Ra)較佳為400nm以下，又較佳為350nm以下，更佳為300nm以下。關於下限並未特別限定，但較佳可設為0.5nm以上，又較佳可設為1nm以上等。又，粗糙化處理後的絕緣層表面的均方平方根粗糙度(Rq)較佳為400nm以下，又較佳為350nm以下，更佳為300nm以下。關於下限並未特別限定，但較佳可設為0.5nm以上，又較佳可設為1nm以上等。絕緣層表面的算術平均粗糙度(Ra)及均方平方根粗糙度(Rq)係可使用非接觸型表面粗糙度計來進行測定。In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening is preferably 400 nm or less, more preferably 350 nm or less, and more preferably 300 nm or less. The lower limit is not particularly limited, but it is preferably 0.5 nm or more, and more preferably 1 nm or more. In addition, the root mean square roughness (Rq) of the surface of the insulating layer after roughening is preferably 400 nm or less, more preferably 350 nm or less, and more preferably 300 nm or less. The lower limit is not particularly limited, but it is preferably 0.5 nm or more, and more preferably 1 nm or more. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

步驟(V)係形成導體層之步驟，其為在絕緣層上來形成導體層。使用作為導體層的導體材料並未特別限定。於適合的實施形態中，導體層係包含選自由金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫及銦所構成之群組之1種以上的金屬。導體層係可以是單質金屬層亦可以是合金層，作為合金層，可舉例如由選自上述群組之2種以上的金屬的合金(例如鎳･鉻合金、銅･鎳合金及銅･鈦合金)所形成的層。其中，就導體層形成的汎用性、成本、圖型化的容易性等的觀點而言，以鉻、鎳、鈦、鋁、鋅、金、鈀、銀或者銅的單質金屬層、或鎳･鉻合金、銅･鎳合金、銅･鈦合金的合金層為較佳，以鉻、鎳、鈦、鋁、鋅、金、鈀、銀或者銅的單質金屬層、或鎳･鉻合金的合金層為又較佳。Step (V) is a step of forming a conductor layer, which is to form the conductor layer on the insulating layer. The conductor material used as the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer includes one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium The above metals. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys of two or more metals selected from the above groups (for example, nickel･chromium alloy, copper･nickel alloy, and copper･titanium alloy). Among them, from the viewpoint of versatility, cost, ease of patterning, etc. of forming the conductor layer, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel･ An alloy layer of chromium alloy, copper･nickel alloy, copper･titanium alloy is preferred, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel･chromium alloy It's better.

導體層係可以是單層構造、亦可以是層合2層以上由不同種類的金屬或者合金所構成的單質金屬層或合金層的多層構造。若導體層為多層構造時，與絕緣層相接的層係以鉻、鋅或者鈦的單質金屬層、或鎳･鉻合金的合金層為較佳。The conductor layer system may have a single-layer structure or a multi-layer structure in which two or more simple metal layers or alloy layers composed of different types of metals or alloys are laminated. If the conductor layer has a multi-layer structure, the layer connected to the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

導體層的厚度係取決於所期望的印刷配線板的設計，一般為3μm～35μm，較佳為5μm～30μm。The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

在一實施形態中，亦可藉由濺鍍法來形成導體層。濺鍍法之中，首先，藉由濺鍍在絕緣層表面形成導體種晶層後，藉由濺鍍在該導體種晶層上形成導體濺鍍層。於藉由濺鍍的導體種晶層的形成之前，亦可藉由反向濺鍍(reverse sputtering)來淨化絕緣層表面。作為該反向濺鍍時所使用的氣體，可使用各種的氣體，但其中以Ar、O2 、N2 為較佳。種晶層若為Cu及Cu合金之情形時，以Ar或O2 或是Ar、O2 混合氣體為較佳；種晶層若為Ti之情形時，以Ar或N2 或是Ar、N2 混合氣體為較佳；種晶層若為Cr及Cr合金(鎳鉻合金等)之情形時，以Ar或O2 或是Ar、O2 混合氣體為較佳。濺鍍係可使用磁控濺鍍、鏡控(mirrortron)濺鍍等的各種濺鍍裝置來進行。作為形成導體種晶層的金屬，可舉例Cr、Ni、Ti、鎳鉻合金等。特別是以Cr、Ti為佳。導體種晶層的厚度，通常而言係以如下述般來形成：較佳為5nm以上，又較佳為10nm以上；較佳為1000nm以下，又較佳為500nm以下。作為形成導體濺鍍層的金屬，可舉例Cu、Pt、Au、Pd等。特別是以Cu為佳。導體濺鍍層的厚度，通常而言係以如下述般來形成：較佳為50nm以上，又較佳為100nm以上；較佳為3000nm以下，又較佳為1000nm以下。In one embodiment, the conductor layer can also be formed by sputtering. In the sputtering method, first, a conductor seed layer is formed on the surface of the insulating layer by sputtering, and then a conductor sputtering layer is formed on the conductor seed layer by sputtering. Before the formation of the conductor seed layer by sputtering, the surface of the insulating layer can also be purified by reverse sputtering. As the gas used in this reverse sputtering, various gases can be used, but among them, Ar, O 2 , and N 2 are preferred. If the seed layer is Cu and Cu alloy, Ar or O 2 or a mixed gas of Ar and O 2 is preferred; if the seed layer is Ti, Ar or N 2 or Ar, N 2 mixed gas is preferred; if the seed layer is Cr and Cr alloy (nickel-chromium alloy, etc.), Ar or O 2 or Ar, O 2 mixed gas is preferred. The sputtering system can be performed using various sputtering devices such as magnetron sputtering and mirrortron sputtering. Examples of the metal forming the conductor seed layer include Cr, Ni, Ti, nickel-chromium alloy, and the like. In particular, Cr and Ti are preferred. The thickness of the conductor seed layer is generally formed as follows: preferably 5 nm or more, more preferably 10 nm or more; preferably 1000 nm or less, further preferably 500 nm or less. Examples of the metal forming the conductor sputtering layer include Cu, Pt, Au, Pd, and the like. In particular, Cu is preferred. The thickness of the conductor sputtering layer is generally formed as follows: preferably 50 nm or more, more preferably 100 nm or more; preferably 3000 nm or less, further preferably 1000 nm or less.

於導體種晶層形成時，形成於絕緣層表面的表面粗度(Ra值)，於藉由蝕刻來將該導體種晶層除去後所測得的值，較佳為150nm以下，較佳以10～150nm的範圍為更佳，更佳10～120nm以下。When the conductor seed layer is formed, the surface roughness (Ra value) formed on the surface of the insulating layer, measured after the conductor seed layer is removed by etching, is preferably 150 nm or less, and is preferably 150 nm or less. A range of 10 to 150 nm is more preferred, and a range of 10 to 120 nm or less is more preferred.

藉由濺鍍法形成導體層後，可進一步藉由電解銅鍍敷在該導體層上形成銅鍍敷層。銅鍍敷層的厚度，通常而言係以如下述般來形成：較佳為5μm以上，又較佳為8μm以上；較佳為75μm以下，又較佳為35μm以下。電路形成時可使用減成法、半加成法等的周知的方法。After the conductor layer is formed by sputtering, a copper plating layer can be further formed on the conductor layer by electrolytic copper plating. The thickness of the copper plating layer is generally formed as follows: preferably 5 μm or more, more preferably 8 μm or more; preferably 75 μm or less, further preferably 35 μm or less. When forming a circuit, well-known methods such as the subtractive method and the semi-additive method can be used.

在其他的一實施形態中，亦可使用金屬箔來形成導體層。使用金屬箔來形成導體層之情形時，步驟(V)係以在步驟(I)與步驟(II)之間來實施為合適。例如，於步驟(I)之後，將支撐體除去，將金屬箔對於已露出的樹脂組成物層的表面進行層合。樹脂組成物層與金屬箔的層合，可藉由真空層合法來實施。層合的條件，可設為和內層基板與樹脂薄片的層合條件為相同。接下來，實施步驟(II)來形成絕緣層。之後，亦可藉由減成法、改良型半加成法等來形成具有所期望的配線圖型的導體層。In another embodiment, metal foil may be used to form the conductor layer. When a metal foil is used to form the conductor layer, step (V) is preferably performed between step (I) and step (II). For example, after step (I), the support is removed, and the metal foil is laminated on the exposed surface of the resin composition layer. The resin composition layer and the metal foil can be laminated by a vacuum lamination method. The conditions for lamination can be the same as the conditions for laminating the inner layer substrate and the resin sheet. Next, step (II) is performed to form an insulating layer. After that, a conductor layer having a desired wiring pattern can also be formed by a subtractive method, a modified semi-additive method, or the like.

金屬箔係可藉由例如電解法、壓延法等的周知的方法來進行製造。作為金屬箔，可舉例如銅箔、鋁箔等，以銅箔為佳。作為銅箔，可使用由銅的單質金屬所構成的箔，亦可使用由銅與其他的金屬(例如錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)的合金所構成的箔。作為金屬箔的市售品，可舉例如JX金屬公司製的HLP箔、JXUT-III箔、三井金屬礦業公司製的3EC-III箔、TP-III箔等。The metal foil can be produced by known methods such as electrolysis and calendering. Examples of the metal foil include copper foil, aluminum foil, and the like, with copper foil being preferred. As the copper foil, a foil composed of copper as a single metal may be used, or a foil composed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. . Examples of commercially available metal foils include HLP foil and JXUT-III foil manufactured by JX Metals Co., Ltd., 3EC-III foil and TP-III foil manufactured by Mitsui Metal Mining Co., Ltd., and the like.

又，在其他的一實施形態中，導體層係可藉由鍍敷來形成。例如藉由半加成法、全加成法等的以往周知的技術，在絕緣層的表面上進行鍍敷，從而可形成具有所期望的配線圖型的導體層，就製造的簡便性之觀點而言，以藉由半加成法來形成為較佳。以下為表示藉由半加成法來形成導體層之例子。In another embodiment, the conductor layer may be formed by plating. For example, by plating the surface of the insulating layer using conventionally known techniques such as the semi-additive method and the fully-additive method, a conductor layer having a desired wiring pattern can be formed. From the viewpoint of ease of production, Generally speaking, it is better to form it by the semi-additive method. The following is an example of forming a conductor layer by the semi-additive method.

首先，藉由無電解鍍敷在絕緣層的表面上形成鍍敷種晶層。接下來，在形成的鍍敷種晶層上，對應所期望的配線圖型，來形成使鍍敷種晶層的一部分露出的遮罩圖型。在露出的鍍敷種晶層上藉由電解鍍敷來形成金屬層後，將遮罩圖型去除。之後，藉由蝕刻等來去除不需要的鍍敷種晶層，從而可形成具有所期望的配線圖型的導體層。First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer in accordance with a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like, thereby forming a conductor layer having a desired wiring pattern.

[半導體裝置] 本發明的半導體裝置為包含本發明的印刷配線板。本發明的半導體裝置係可使用本發明的印刷配線板來製造。[Semiconductor device] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

作為半導體裝置，可舉出供於電氣製品(例如電腦、行動電話、數位相機及電視等)及交通工具(例如摩托車、汽車、電車、船舶及飛機等)等的各種半導體裝置。Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and airplanes).

本發明的半導體裝置係可藉由在印刷配線板的導通部位安裝零件(半導體晶片)來製造。所謂的「導通部位」，係指「印刷配線板中之傳遞電信號的部位」，其位置可以是表面、或被埋入的部位均可。又，半導體晶片只要是將半導體作為材料的電氣電路元件即可，並未特別限定。The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The so-called "conducting part" refers to the "part of the printed wiring board that transmits electrical signals", and its location can be on the surface or a buried part. In addition, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

製造半導體裝置時的半導體晶片的安裝方法，只要使半導體晶片有效地發揮功能即可，並未特別限定，但具體而言可舉出導線接合安裝方法、倒裝晶片安裝方法、藉由無凸塊增層(BBUL)之安裝方法、藉由異向性導電薄膜(ACF)之安裝方法、藉由非導電性薄膜(NCF)之安裝方法等。於此，所謂的「藉由無凸塊增層(BBUL)之安裝方法」，係指「將半導體晶片直接埋置在印刷配線板的凹部，使半導體晶片與印刷配線板上的配線連接之安裝方法」。 [實施例]The mounting method of the semiconductor chip when manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip can effectively function. However, specific examples include wire bonding mounting method, flip chip mounting method, and bumpless mounting method. The installation method of build-up layer (BBUL), the installation method of anisotropic conductive film (ACF), the installation method of non-conductive film (NCF), etc. Here, the so-called "mounting method by bump-less build-up (BBUL)" refers to "mounting in which the semiconductor chip is directly embedded in the recessed portion of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board. method". [Example]

以下為表示出實施例來對於本發明進行具體說明。但，本發明並不受以下之實施例的限定。於以下之說明中，表示量的「份」及「%」，只要沒有特別說明，分別代表「質量份」及「質量%」之涵義。又，以下所說明的操作，只要是沒有特別說明係指在常溫常壓的環境下來進行。The present invention will be described in detail below by showing examples. However, the present invention is not limited to the following examples. In the following description, "parts" and "%" expressing amounts, unless otherwise specified, represent "parts by mass" and "% by mass" respectively. In addition, the operations described below are performed in an environment of normal temperature and pressure unless otherwise specified.

[絕緣層與導體層的密著強度(剝離強度)的測定] ＜評估基板A的製作＞ (1)內層電路基板的基底處理 將形成有內層電路的玻璃布基材環氧樹脂兩面覆銅層合板(銅箔的厚度18μm、基板厚度0.4mm、Panasonic公司製「R1515A」)的兩面，以微蝕刻劑(MEC公司製「CZ8101」)蝕刻1μm，來進行銅表面的粗糙化處理。[Measurement of the adhesion strength (peel strength) of the insulating layer and the conductor layer] ＜Preparation of Evaluation Board A＞ (1) Base treatment of inner circuit substrate Both sides of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, "R1515A" manufactured by Panasonic Corporation) with an inner circuit formed thereon were coated with a micro-etching agent ("MCC Corporation" CZ8101") etches 1μm to roughen the copper surface.

(2)樹脂薄片的層合 將實施例及比較例所製作的樹脂薄片a，使用分批式真空加壓貼合機(名機製作所公司製「MVLP-500」)，以樹脂組成物層與內層電路基板接觸之方式，來層合至內層電路基板的兩面。層合係藉由以減壓30秒鐘後將氣壓設為13hPa以下，之後，藉由以100℃、壓力0.74MPa來進行30秒鐘的層合處理。(2)Lamination of resin sheets The resin sheet a produced in the Examples and Comparative Examples was used in a batch-type vacuum pressure laminating machine ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) to bring the resin composition layer into contact with the inner circuit substrate. to be laminated to both sides of the inner circuit substrate. The lamination system is performed by reducing the pressure for 30 seconds and then setting the air pressure to 13 hPa or less, and then performing a lamination process at 100° C. and a pressure of 0.74 MPa for 30 seconds.

(3)樹脂組成物層的硬化 將經層合的樹脂薄片a，以100℃、30分鐘、接下來以170℃、30分鐘進行加熱，來使樹脂組成物層熱硬化而形成絕緣層。(3) Hardening of the resin composition layer The laminated resin sheet a was heated at 100°C for 30 minutes and then at 170°C for 30 minutes to thermally harden the resin composition layer to form an insulating layer.

(4)藉由UV-YAG雷射的通孔的形成 將支撐體剝離後，使絕緣層的表面露出，使用UV-YAG雷射加工機(Via Mechanics公司製「LU-2L212/M50L」)並以下述條件，來將通孔形成至絕緣層。 條件：能量0.30W、投射數25、目標頂部孔徑30μm(4) Formation of through holes by UV-YAG laser After peeling off the support, the surface of the insulating layer was exposed, and a through hole was formed in the insulating layer using a UV-YAG laser processing machine ("LU-2L212/M50L" manufactured by Via Mechanics) under the following conditions. Conditions: Energy 0.30W, projection number 25, target top aperture 30μm

(5)乾式除膠渣處理 於通孔的形成後，將形成有絕緣層的內層電路基板使用真空電漿蝕刻裝置(Tepla公司製100-E PLASMA SYSTEM)，以O2 /CF4 (混合氣體比)＝25/75、真空度100Pa的條件下進行5分鐘的處理。(5) Dry desmear treatment After the formation of the through hole, use a vacuum plasma etching device (100-E PLASMA SYSTEM manufactured by Tepla Corporation) on the inner circuit substrate with the insulating layer formed, and use O 2 /CF 4 (mixed The gas ratio) = 25/75 and the vacuum degree is 100 Pa, and the process is performed for 5 minutes.

(6)藉由乾式法的導體層的形成 使用濺鍍裝置(Canon ANELVA公司製「E-400S」)，在絕緣層上形成鈦層(厚度30nm)，接下來形成銅層(厚度300nm)。將得到的基板以150℃加熱30分鐘來進行退火處理後，依據半加成法，藉由形成蝕刻阻劑、曝光･顯影的圖型形成之後，進行硫酸銅電解鍍敷，而形厚度25μm的導體層。導體圖型形成後，以200℃加熱60分鐘來進行退火處理。將得到的印刷配線板稱為「評估基板A」。(6) Formation of conductor layer by dry method Using a sputtering device ("E-400S" manufactured by Canon ANELVA Co., Ltd.), a titanium layer (thickness 30 nm) was formed on the insulating layer, and then a copper layer (thickness 300 nm) was formed. The obtained substrate was annealed by heating at 150°C for 30 minutes. After pattern formation by forming an etching resist, exposure and development according to the semi-additive method, copper sulfate electrolytic plating was performed to form a 25 μm thick plate. conductor layer. After the conductor pattern is formed, annealing is performed by heating at 200°C for 60 minutes. The obtained printed wiring board is called "evaluation board A".

＜剝離強度(剝離強度)的測定＞ 絕緣層與導體層的剝離強度的測定為依據JIS C6481，對於評估基板A來進行。具體而言，在評估基板A的導體層上置入寬10mm、長度100mm的部分的切口，將該一端剝下，並利用夾片器夾住，在室溫中，測定以50mm/分鐘的速度下、沿著垂直方向撕剝35mm時的荷重(kgf/cm)，來求得剝離強度。測定為使用拉伸試驗機(TSE公司製「AC-50C-SL」)。<Measurement of Peel Strength (Peel Strength)> The measurement of the peel strength of the insulating layer and the conductor layer was performed on the evaluation substrate A in accordance with JIS C6481. Specifically, a cutout with a width of 10 mm and a length of 100 mm was placed on the conductor layer of the evaluation substrate A, and one end was peeled off, clamped with a clamp, and measured at a speed of 50 mm/min at room temperature. Next, the load (kgf/cm) when peeling 35mm along the vertical direction is used to determine the peeling strength. The measurement is performed using a tensile testing machine ("AC-50C-SL" manufactured by TSE Corporation).

[介電正切的測定] ＜評估用硬化物B的製作＞ 將實施例及比較例製作的樹脂薄片a以200℃加熱90分鐘來使樹脂組成物層熱硬化後，將支撐體剝離。將得到的硬化物稱為「評估用硬化物B」。[Measurement of dielectric tangent] ＜Preparation of hardened material B for evaluation＞ The resin sheet a produced in Examples and Comparative Examples was heated at 200° C. for 90 minutes to thermally harden the resin composition layer, and then the support was peeled off. The obtained hardened material is called "hardened material for evaluation B".

＜介電正切的測定＞ 將評估用硬化物B切斷成寬2mm、長度80mm的試片。對於該試片使用安捷倫科技(Agilent Technologies)公司製「HP8362B」並以空腔共振擾動法(cavity resonance perturbation method)，以測定頻率5.8GHz、測定溫度23℃下來測定介電正切。對於2個的試片進行測定，並算出其平均值。<Measurement of dielectric tangent> The hardened material B for evaluation was cut into a test piece with a width of 2 mm and a length of 80 mm. For this test piece, "HP8362B" manufactured by Agilent Technologies was used to measure the dielectric tangent using the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Two test pieces were measured and their average value was calculated.

[透濕係數的測定] ＜測定･評估用樣品的調製＞ 將實施例及比較例製作的樹脂薄片b以200℃加熱90分鐘來使樹脂組成物層熱硬化後，將支撐體剝離。將得到的硬化物稱為「評估用硬化物C」。[Measurement of water vapor permeability coefficient] ＜Preparation of samples for measurement and evaluation＞ The resin sheet b prepared in Examples and Comparative Examples was heated at 200° C. for 90 minutes to thermally harden the resin composition layer, and then the support was peeled off. The obtained hardened material is called "hardened material for evaluation C".

＜透濕係數的測定＞ 將評估用硬化物C切斷成直徑70mm的圓狀，依據JIS Z0208的透濕度試驗方法(杯法(cup method))來進行透濕度的測定。具體而言，以60℃、85%RH、24小時放置樣品，測定透過該樣品的水分重量，藉此來求得透濕度(g/m2 ･24h)，除以膜厚後，而算出透濕係數(g/mm･m2 ･24h)。以3個試片的平均值來算出。<Measurement of water vapor permeability coefficient> The cured material C for evaluation was cut into a circular shape with a diameter of 70 mm, and the water vapor permeability was measured in accordance with the water vapor permeability test method (cup method) of JIS Z0208. Specifically, the sample is placed at 60°C, 85%RH for 24 hours, and the weight of water that passes through the sample is measured to determine the moisture permeability (g/m 2 ･24h). The permeability is calculated by dividing by the film thickness. Moisture coefficient (g/mm･m 2 ･24h). Calculated as the average of 3 test pieces.

[高溫高濕環境試驗後的絕緣可靠性的評估、導體層間的絕緣層的厚度的測定] ＜評估用基板D的調製＞ (1)內層電路基板的基底處理 作為內層電路基板，準備兩面具有以1mm見方格子的配線圖型(殘銅率70%)來形成電路導體(銅)的玻璃布基材環氧樹脂兩面覆銅層合板(銅箔的厚度18μm、基板的厚度0.4mm、Panasonic公司製「R1515A」)。將該內層電路基板的兩面浸漬於微蝕刻劑(MEC公司製「CZ8101」)中來進行銅表面的粗糙化處理(銅蝕刻量0.7μm)。[Evaluation of insulation reliability after high temperature and high humidity environment test, measurement of thickness of insulation layer between conductor layers] <Modulation of Evaluation Substrate D> (1) Base treatment of inner circuit substrate As the inner circuit board, prepare a glass cloth-based epoxy resin double-sided copper-clad laminate (thickness of copper foil: 18 μm) with circuit conductors (copper) formed on both sides in a 1 mm square grid wiring pattern (remaining copper rate: 70%) , substrate thickness 0.4mm, "R1515A" manufactured by Panasonic Corporation). Both surfaces of the inner layer circuit board were immersed in a microetchant ("CZ8101" manufactured by MEC Corporation) to roughen the copper surface (copper etching amount: 0.7 μm).

(2)樹脂薄片的層合 將實施例及比較例製作的樹脂薄片c，使用分批式真空加壓貼合機(Nikko-Materials公司製、2階段增層貼合機、CVP700)，以樹脂組成物層與內層電路基板接觸之方式，來層合至內層電路基板的兩面。層合係藉由以減壓30秒鐘後將氣壓設為13hPa以下，再以120℃、壓力0.74MPa來進行30秒鐘的壓黏而來進行。接下來，以120℃、壓力0.5MPa來進行60秒鐘的熱壓(hot press)。(2)Lamination of resin sheets The resin sheet c produced in the Examples and Comparative Examples was bonded with the resin composition layer and the inner circuit substrate using a batch-type vacuum pressure laminating machine (Nikko-Materials Co., Ltd., 2-stage build-up laminating machine, CVP700). Contact method to laminate to both sides of the inner circuit substrate. Lamination is performed by reducing the pressure for 30 seconds, setting the air pressure to 13hPa or less, and then performing pressure bonding at 120°C and a pressure of 0.74MPa for 30 seconds. Next, hot press was performed at 120° C. and a pressure of 0.5 MPa for 60 seconds.

(3)樹脂組成物層的硬化 將層合有樹脂薄片c的內層電路基板，以100℃、30分鐘、接下來以170℃、30分鐘進行加熱，來使樹脂組成物層熱硬化而形成絕緣層。(3) Hardening of the resin composition layer The inner circuit board on which the resin sheet c was laminated was heated at 100° C. for 30 minutes and then at 170° C. for 30 minutes to thermally harden the resin composition layer to form an insulating layer.

(4)藉由UV-YAG雷射的通孔的形成 將支撐體剝離後，使絕緣層的表面露出，使用UV-YAG雷射加工機(Via Mechanics公司製「LU-2L212/M50L」)並以在內層電路基板的電路導體上開口之方式，利用下述條件，來將通孔形成至絕緣層。 條件：能量0.30W、投射數25、目標頂部孔徑30μm(4) Formation of through holes by UV-YAG laser After peeling off the support, the surface of the insulating layer was exposed, and a UV-YAG laser processing machine ("LU-2L212/M50L" manufactured by Via Mechanics) was used to open the circuit conductor of the inner circuit board. The following conditions are used to form via holes to the insulating layer. Conditions: Energy 0.30W, projection number 25, target top aperture 30μm

(5)乾式除膠渣處理 於通孔的形成後，將形成有絕緣層的內層電路基板使用真空電漿蝕刻裝置(Tepla公司製100-E PLASMA SYSTEM)，以O2 /CF4 (混合氣體比)＝25/75、真空度100Pa的條件下進行5分鐘的處理。(5) Dry desmear treatment After the formation of the through hole, use a vacuum plasma etching device (100-E PLASMA SYSTEM manufactured by Tepla Corporation) on the inner circuit substrate with the insulating layer formed, and use O 2 /CF 4 (mixed The gas ratio) = 25/75 and the vacuum degree is 100 Pa, and the process is performed for 5 minutes.

(6)藉由乾式法的導體層的形成 使用濺鍍裝置(Canon ANELVA公司製「E-400S」)來形成鈦層(厚度30nm)，接下來形成銅層(厚度300nm)。將得到的基板以150℃加熱30分鐘，來進行退火處理。(6) Formation of conductor layer by dry method A titanium layer (thickness 30 nm) was formed using a sputtering device ("E-400S" manufactured by Canon ANELVA Co., Ltd.), and then a copper layer (thickness 300 nm) was formed. The obtained substrate was heated at 150° C. for 30 minutes to perform annealing treatment.

(7)電解鍍敷 接下來，使用Atotech Japan公司製的藥液，以於通孔內為填充銅之條件下來進行電解銅鍍敷步驟。之後，作為用來以蝕刻予以圖型化的阻劑圖型，使用下述焊盤(land)圖型及圓形導體圖型，以10μm的厚度在絕緣層的表面上形成具有焊盤及導體圖型的導體層，前述焊盤圖型：透過通孔來與下層導體(即，內層電路基板的電路導體)導通的直徑1mm的焊盤圖型；前述導體圖型：和前述下層導體未連接的直徑10mm的圓形導體圖型。接著，以200℃、90分鐘來進行退火處理。將該基板稱為評估用基板D。(7)Electrolytic plating Next, an electrolytic copper plating step is performed using a chemical solution manufactured by Atotech Japan under the condition that the through holes are filled with copper. After that, as a resist pattern for patterning by etching, the following land pattern and circular conductor pattern are used to form a land and conductor with a thickness of 10 μm on the surface of the insulating layer. Patterned conductor layer, the aforementioned pad pattern: a 1 mm diameter pad pattern that is connected to the lower conductor (i.e., the circuit conductor of the inner circuit substrate) through the through hole; the aforementioned conductor pattern: and the aforementioned lower conductor are not Connected circular conductor pattern of 10mm diameter. Next, annealing treatment was performed at 200° C. for 90 minutes. This substrate is called evaluation substrate D.

＜導體層間的絕緣層的厚度的測定＞ 將評估用基板D使用FIB-SEM複合裝置(SII NanoTechnology公司製「SMI3050SE」)進行斷面觀察。詳細而言，以FIB(聚焦離子束)來切出垂直於導體層表面的方向的斷面，從斷面SEM圖像來測定導體層間的絕緣層厚。對於各樣品，觀察隨機選出的5部位的斷面SEM圖像，以其平均值定為導體層間的絕緣層的厚度。<Measurement of the thickness of the insulating layer between conductor layers> Use the FIB-SEM hybrid device (SII "SMI3050SE" manufactured by NanoTechnology Co., Ltd.) was used for cross-sectional observation. Specifically, a cross section perpendicular to the surface of the conductor layer was cut using FIB (focused ion beam), and the thickness of the insulating layer between the conductor layers was measured from the cross-sectional SEM image. For each sample, cross-sectional SEM images of five randomly selected locations were observed, and the average value was determined as the thickness of the insulating layer between the conductor layers.

＜絕緣層的高溫高濕環境試驗後的絕緣可靠性的評估＞ 以上述得到的評估用基板D的直徑10mm的圓形導體側為+電極，以和直徑1mm的焊盤連接的內層電路基板的電路導體(銅)側為-電極，使用高度加速壽命試驗裝置(ETAC公司製「PM422」)，以130℃、85%相對濕度、3.3V直流電壓施加之條件下進行500小時的試驗，再以電化學遷移試驗機(J-RAS公司製「ECM-100」)測定該500小時經過後的絕緣電阻值。重複進行該測定6次，並算出平均值。又，以6次試片全部的電阻值為107 Ω以上時，評估為「○」；只要有1次未滿107 Ω時，則評估為「×」。<Evaluation of insulation reliability after high-temperature and high-humidity environment test of the insulation layer> An inner-layer circuit board connected to a 1mm-diameter pad using the 10mm-diameter circular conductor side of the evaluation substrate D obtained above as the + electrode. The conductor (copper) side of the circuit is the -electrode. Using a highly accelerated life test device ("PM422" manufactured by ETAC Corporation), the test was conducted for 500 hours under the conditions of 130°C, 85% relative humidity, and 3.3V DC voltage application, and then The insulation resistance value after the passage of 500 hours was measured with an electrochemical migration tester ("ECM-100" manufactured by J-RAS Corporation). This measurement was repeated 6 times, and the average value was calculated. In addition, if the resistance value of all test pieces is 10 7 Ω or more for 6 times, the evaluation is "○"; if the resistance value is less than 10 7 Ω even once, the evaluation is "×".

[實施例1] 將雙酚AF型環氧樹脂(三菱化學公司製「YL7760」、環氧當量約238)15份、苯乙烯系彈性體(旭化成公司製氫化苯乙烯系熱可塑性彈性體「Tuftec H1043」、苯乙烯含量67%)3份，在甲苯25份、MEK15份中一邊攪拌一邊使其加熱溶解。冷卻至室溫後，對此混合具有乙烯基苯基的樹脂(Mitsubishi Gas Chemical公司製「OPE-2St」、數平均分子量1200、不揮發分65質量%的甲苯溶液)46份、具有(甲基)丙烯醯基的樹脂(新中村化學工業公司製「NK Ester A-DOG」、分子量326)30份、活性酯型硬化劑(DIC公司製「HPC8000-65T」、固形分65質量%的甲苯溶液)30份、含有三嗪骨架的酚系硬化劑(DIC公司製「LA-3018-50P」、羥基當量約151的固形分50%的2-甲氧基丙醇溶液)4份、碳二亞胺系硬化劑(Nisshinbo chemical公司製「V-03」、活性基當量約216、固形分50質量%的甲苯溶液)8份、硬化促進劑(N,N-二甲基-4-胺基砒啶(DMAP)、固形分5質量%的MEK溶液)6份、聚合起始劑(日油公司製「Perbutyl C」)1份、經苯基胺基矽烷系偶合劑(信越化學工業公司製、「KBM573」)進行表面處理的球形二氧化矽(平均粒徑0.5μm、比表面積5.9m2 /g、Admatechs公司製「SO-C2」)250份，利用高速旋轉混合機均勻地分散後，來製作樹脂清漆。[Example 1] 15 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: approximately 238), styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Tuftec" manufactured by Asahi Kasei Corporation) H1043", styrene content 67%), add 25 parts of toluene and 15 parts of MEK to heat and dissolve while stirring. After cooling to room temperature, 46 parts of a resin having a vinyl phenyl group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a number average molecular weight of 1,200 and a non-volatile content of 65% by mass) and (methyl ) 30 parts of acryl-based resin ("NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326), active ester type hardener ("HPC8000-65T" manufactured by DIC Corporation, toluene solution with a solid content of 65% by mass) ), 30 parts of a phenolic hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, a 50% solid content 2-methoxypropanol solution with a hydroxyl equivalent of about 151), 4 parts of carbodioxide 8 parts of amine hardener ("V-03" manufactured by Nisshinbo Chemical, toluene solution with active group equivalent of about 216 and solid content of 50% by mass), hardening accelerator (N,N-dimethyl-4-aminoarsenic 6 parts of MEK solution with 5% solid content by mass), 1 part of polymerization initiator ("Perbutyl C" manufactured by NOF Corporation), phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd. "KBM573") surface-treated spherical silica (average particle diameter 0.5 μm, specific surface area 5.9 m 2 /g, Admatechs Co., Ltd. "SO-C2") 250 parts, dispersed uniformly using a high-speed rotary mixer, Make resin varnish.

接下來，在附有脫模處理的聚對苯二甲酸乙二醇酯薄膜(LINTEC公司製「AL5」、厚度38μm)的脫模面上，以乾燥後的樹脂組成物層的厚度成為20μm之方式來均勻地塗布樹脂清漆，以80～120℃(平均100℃)使其乾燥3分鐘，來製作樹脂薄片a。Next, on the release surface of a polyethylene terephthalate film ("AL5" manufactured by LINTEC, thickness 38 μm) with release treatment, the thickness of the dried resin composition layer was reduced to 20 μm. method to evenly apply the resin varnish and dry it at 80 to 120°C (average 100°C) for 3 minutes to produce a resin sheet a.

又，作為透濕係數測定用，在附有脫模處理的聚對苯二甲酸乙二醇酯薄膜(LINTEC公司製「AL5」、厚度38μm)的脫模面上，以乾燥後的樹脂組成物層的厚度成為40μm之方式來均勻地塗布樹脂清漆，以80～120℃(平均100℃)使其乾燥4分鐘，來製作樹脂薄片b。In addition, for measuring the moisture permeability coefficient, the dried resin composition was used on the release surface of a release-treated polyethylene terephthalate film ("AL5" manufactured by LINTEC, thickness 38 μm). The resin varnish is uniformly applied so that the thickness of the layer becomes 40 μm, and dried at 80 to 120° C. (average 100° C.) for 4 minutes to prepare a resin sheet b.

作為高溫高濕環境試驗後的絕緣可靠性的評估用，在附有脫模處理的聚對苯二甲酸乙二醇酯薄膜(LINTEC公司製「AL5」、厚度38μm)的脫模面上，以乾燥後的樹脂組成物層的厚度成為10μm之方式來均勻地塗布樹脂清漆，以80℃使其乾燥2分鐘，來製作樹脂薄片c。For evaluation of insulation reliability after high-temperature and high-humidity environment testing, on the release surface of a release-treated polyethylene terephthalate film ("AL5" manufactured by LINTEC, thickness 38 μm), The resin varnish was evenly applied so that the thickness of the dried resin composition layer became 10 μm, and dried at 80° C. for 2 minutes to prepare a resin sheet c.

[實施例2] 將聯苯型環氧樹脂(日本化藥公司製「NC3000L」、環氧當量約269)5份、雙酚AF型環氧樹脂(三菱化學公司製「YL7760」、環氧當量約238)10份、苯乙烯系彈性體(旭化成公司製氫化苯乙烯系熱可塑性彈性體「Tuftec P2000」、苯乙烯含量67%)20份、苯乙烯系彈性體(Daicel公司製環氧化苯乙烯-丁二烯熱可塑性彈性體「Epofriend AT501」、苯乙烯含量40%)20份，在甲苯50份、MEK20份中一邊攪拌一邊使其加熱溶解。冷卻至室溫後，對此混合具有乙烯基苯基的樹脂(Mitsubishi Gas Chemical公司製「OPE-2St」、數平均分子量1200、不揮發分65質量%的甲苯溶液)92份、具有(甲基)丙烯醯基的樹脂(新中村化學工業公司製「NK Ester A-DOG」、分子量326)30份、活性酯型硬化劑(DIC公司製「EXB9416-70BK」、活性基當量約330的不揮發分70質量%的甲基異丁基酮溶液)28份、含有三嗪骨架的酚系硬化劑(DIC公司製「LA-3018-50P」、羥基當量約151的固形分50%的2-甲氧基丙醇溶液)4份、碳二亞胺系硬化劑(Nisshinbo chemical公司製「V-03」、活性基當量約216、固形分50質量%的甲苯溶液)8份、硬化促進劑(N,N-二甲基-4-胺基砒啶(DMAP)、固形分5質量%的MEK溶液)6份、聚合起始劑(日油公司製「Perbutyl C」)1份、經苯基胺基矽烷系偶合劑(信越化學工業公司製、「KBM573」)進行表面處理的球狀二氧化矽(平均粒徑0.3μm、比表面積30.7m2 /g、Denka公司製「UFP-30」)200份，利用高速旋轉混合機均勻地分散後，來製作樹脂清漆，並與實施例1相同地來製作樹脂薄片a～c。[Example 2] 5 parts of biphenyl-type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent weight: about 269), bisphenol AF-type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent Approximately 238) 10 parts of styrenic elastomer (hydrogenated styrenic thermoplastic elastomer "Tuftec P2000" manufactured by Asahi Kasei Corporation, styrene content 67%), 20 parts of styrenic elastomer (epoxidized styrene manufactured by Daicel Corporation - 20 parts of butadiene thermoplastic elastomer "Epofriend AT501", styrene content 40%) are heated and dissolved in 50 parts of toluene and 20 parts of MEK while stirring. After cooling to room temperature, 92 parts of a resin having a vinyl phenyl group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a number average molecular weight of 1,200 and a non-volatile content of 65% by mass) and (methyl ) 30 parts of acryl-based resin ("NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326), active ester type hardener ("EXB9416-70BK" manufactured by DIC Corporation, non-volatile active group equivalent of about 330 28 parts of a 70 mass% methyl isobutyl ketone solution), a phenolic hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, and 50% solid content of 2-methane with a hydroxyl equivalent of about 151 Oxypropanol solution) 4 parts, carbodiimide hardener (Nisshinbo Chemical Co., Ltd. "V-03", active group equivalent of about 216, solid content 50 mass% toluene solution) 8 parts, hardening accelerator (N , 6 parts of N-dimethyl-4-aminopyridine (DMAP), MEK solution with a solid content of 5% by mass), 1 part of polymerization initiator ("Perbutyl C" manufactured by NOF Corporation), and phenylamine Spherical silica (average particle diameter 0.3 μm, specific surface area 30.7 m 2 /g, Denka Co., Ltd. "UFP-30") surface-treated with a silane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 200 parts were uniformly dispersed using a high-speed rotating mixer to prepare a resin varnish, and resin sheets a to c were prepared in the same manner as in Example 1.

[比較例1] 在實施例1中，將具有乙烯基苯基的樹脂(Mitsubishi Gas Chemical公司製「OPE-2St」、數平均分子量1200、不揮發分65質量%的甲苯溶液)的量從46份變更成92份，且未使用(甲基)丙烯酸酯(新中村化學工業公司製「NK Ester A-DOG」、分子量326)30份。除了上述事項以外其餘與實施例1相同地來製作樹脂清漆、樹脂薄片a～c。[Comparative example 1] In Example 1, the amount of the resin having a vinyl phenyl group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a number average molecular weight of 1,200 and a non-volatile content of 65% by mass) was changed from 46 parts to 92 parts. , and 30 parts of (meth)acrylate ("NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326) was not used. Resin varnish and resin sheets a to c were produced in the same manner as in Example 1 except for the above-mentioned matters.

[比較例2] 在實施例1中，未使用苯乙烯系彈性體(旭化成公司製氫化苯乙烯系熱可塑性彈性體「Tuftec H1043」、苯乙烯含量67%)3份。除了上述事項以外其餘與實施例1相同地來製作樹脂清漆、樹脂薄片a～c。[Comparative example 2] In Example 1, 3 parts of styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Tuftec H1043" manufactured by Asahi Kasei Co., Ltd., styrene content: 67%) was not used. Resin varnish and resin sheets a to c were produced in the same manner as in Example 1 except for the above-mentioned matters.

[比較例3] 在實施例2中，將具有乙烯基苯基的樹脂(Mitsubishi Gas Chemical公司製「OPE-2St」、數平均分子量1200、不揮發分65質量%的甲苯溶液)的量從92份變更成138份，且未使用(甲基)丙烯酸酯(新中村化學工業公司製「NK Ester A-DOG」、分子量326)30份。除了上述事項以外其餘與實施例2相同地來製作樹脂清漆、樹脂薄片a～c。[Comparative example 3] In Example 2, the amount of the resin having a vinyl phenyl group ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., a toluene solution with a number average molecular weight of 1,200 and a non-volatile content of 65% by mass) was changed from 92 parts to 138 parts. , and 30 parts of (meth)acrylate ("NK Ester A-DOG" manufactured by Shin-Nakamura Chemical Industry Co., Ltd., molecular weight 326) was not used. Resin varnish and resin sheets a to c were produced in the same manner as in Example 2 except for the above-mentioned matters.

[比較例4] 在實施例2中，未使用苯乙烯系彈性體(旭化成公司製氫化苯乙烯系熱可塑性彈性體「Tuftec P2000」、苯乙烯含量67%)20份，且未使用苯乙烯系彈性體(Daicel公司製環氧化苯乙烯-丁二烯熱可塑性彈性體「Epofriend AT501」、苯乙烯含量40%)20份。除了上述事項以外其餘與實施例2相同地來製作樹脂清漆、樹脂薄片a～c。[Comparative example 4] In Example 2, 20 parts of styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Tuftec P2000" manufactured by Asahi Kasei Co., Ltd., styrene content 67%) was not used, and no styrene-based elastomer (Daicel Co., Ltd. Prepare 20 parts of epoxidized styrene-butadiene thermoplastic elastomer "Epofriend AT501", styrene content 40%). Resin varnish and resin sheets a to c were produced in the same manner as in Example 2 except for the above-mentioned matters.

實施例1～2中，即便是未含有(D-2)成分～(H)成分之情形，雖然程度上會有差異，但確認會總結與上述實施例為相同的結果。In Examples 1 and 2, even when components (D-2) to (H) are not contained, it was confirmed that the same results as in the above-mentioned Examples were obtained, although there were differences in degree.

Claims (14)

一種樹脂組成物，其特徵為包含：(A)環氧樹脂、(B)硬化劑、(C)苯乙烯系彈性體及(D-1)具有(甲基)丙烯醯基的樹脂，其中，將樹脂組成物中的不揮發成分設為100質量%時，(A)成分的含量為1質量%以上15質量%以下，將樹脂組成物中的不揮發成分設為100質量%時，(B)成分的含量為1質量%以上15質量%以下，將樹脂組成物中的不揮發成分設為100質量%時，(C)成分的含量為0.5質量%以上10.76質量%以下，將樹脂組成物中的不揮發成分設為100質量%時，(D-1)成分的含量為5質量%以上50質量%以下，(B)成分為選自活性酯系硬化劑、酚系硬化劑、萘酚系硬化劑、苯并噁嗪系硬化劑、氰酸酯系硬化劑、碳二亞胺系硬化劑、胺系硬化劑及酸酐系硬化劑中的1種以上，(D-1)成分包含下述式(1)表示的樹脂，
Figure 108125420-A0305-02-0069-1
 (式(1)中，R1及R4分別獨立表示(甲基)丙烯醯基，R2及R3分別獨立表示伸烯基、伸芳基、伸雜芳基、-C(=O)O-、-O-、-NHC(=O)-、-NC(=O)N-、-NHC(=O)O-、-C(=O)- 、-S-、-SO-或-NH-，環A表示2價的環狀基)。 A resin composition characterized by containing: (A) epoxy resin, (B) hardener, (C) styrene elastomer and (D-1) resin with (meth)acrylyl group, wherein, When the non-volatile component in the resin composition is 100 mass %, the content of component (A) is 1 mass % or more and 15 mass % or less. When the non-volatile component in the resin composition is 100 mass %, (B) When the content of component (C) is 1% by mass or more and 15% by mass or less and the non-volatile components in the resin composition are 100% by mass, the content of component (C) is 0.5% by mass or more and 10.76% by mass or less. When the non-volatile component in is 100% by mass, the content of component (D-1) is 5% by mass or more and 50% by mass or less, and component (B) is selected from the group consisting of active ester-based hardeners, phenol-based hardeners, and naphthols. Component (D-1) contains one or more of the following hardeners, benzoxazine-based hardeners, cyanate ester-based hardeners, carbodiimide-based hardeners, amine-based hardeners, and acid anhydride-based hardeners. The resin represented by formula (1),
Figure 108125420-A0305-02-0069-1
 (In formula (1), R 1 and R 4 independently represent a (meth)acrylyl group, R 2 and R 3 respectively independently represent an alkenylene group, an aryl group, a heteroaryl group, or -C(=O) O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-or- NH-, ring A represents a divalent cyclic group). 一種樹脂組成物，其特徵為包含：(A)環氧樹脂、(B)硬化劑、(C)苯乙烯系彈性體及(D)具有自由基聚合性不飽和基的樹脂，其中，將樹脂組成物中的不揮發成分設為100質量%時，(A)成分的含量為1質量%以上15質量%以下，將樹脂組成物中的不揮發成分設為100質量%時，(B)成分的含量為1質量%以上15質量%以下，將樹脂組成物中的不揮發成分設為100質量%時，(C)成分的含量為0.5質量%以上10.76質量%以下，將樹脂組成物中的不揮發成分設為100質量%時，(D)成分的含量為5質量%以上50質量%以下，將樹脂組成物以200℃熱硬化90分鐘而得到的硬化物的透濕係數為0g/mm．m2．24h以上10g/mm．m2．24h以下，(B)成分為選自活性酯系硬化劑、酚系硬化劑、萘酚系硬化劑、苯并噁嗪系硬化劑、氰酸酯系硬化劑、碳二亞胺系硬化劑、胺系硬化劑及酸酐系硬化劑中的1種以上，(D)成分包含(D-1)具有(甲基)丙烯醯基的樹脂，(D-1)成分包含下述式(1)表示的樹脂，
Figure 108125420-A0305-02-0070-2
 (式(1)中，R1及R4分別獨立表示(甲基)丙烯醯基，R2及R3分別獨立表示伸烯基、伸芳基、伸雜芳基、-C(=O)O-、-O-、-NHC(=O)-、-NC(=O)N-、-NHC(=O)O-、-C(=O)-、-S-、-SO-或-NH-，環A表示2價的環狀基)。 A resin composition characterized by comprising: (A) epoxy resin, (B) hardener, (C) styrenic elastomer and (D) resin having a radically polymerizable unsaturated group, wherein the resin When the non-volatile component in the composition is 100 mass %, the content of component (A) is 1 mass % or more and 15 mass % or less. When the non-volatile component in the resin composition is 100 mass %, the content of component (B) The content of component (C) is 0.5 mass% or more and 10.76 mass% or less when the non-volatile components in the resin composition are set to 100 mass%. When the non-volatile content is 100% by mass, the content of component (D) is 5% by mass or more and 50% by mass or less, and the cured product obtained by thermally curing the resin composition at 200°C for 90 minutes has a moisture permeability coefficient of 0g/mm. ． m 2 ． 10g/mm over 24h. m 2 ． 24 hours or less, component (B) is selected from active ester hardeners, phenol hardeners, naphthol hardeners, benzoxazine hardeners, cyanate ester hardeners, carbodiimide hardeners, One or more types of amine-based hardeners and acid anhydride-based hardeners, the component (D) contains (D-1) a resin having a (meth)acrylyl group, and the component (D-1) contains the following formula (1) of resin,
Figure 108125420-A0305-02-0070-2
 (In formula (1), R 1 and R 4 independently represent a (meth)acrylyl group, R 2 and R 3 respectively independently represent an alkenylene group, an aryl group, a heteroaryl group, or -C(=O) O-, -O-, -NHC(=O)-, -NC(=O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO- or - NH-, ring A represents a divalent cyclic group). 如請求項1或2之樹脂組成物，其中，(D-1)成分的數平均分子量為3000以下。 The resin composition of Claim 1 or 2, wherein the number average molecular weight of the component (D-1) is 3,000 or less. 如請求項1或2之樹脂組成物，其中，將(C)成分設為100質量%時，(C)成分中包含61質量%以上的苯乙烯單位的含量。 The resin composition of claim 1 or 2, wherein the component (C) contains a content of styrene units of 61 mass% or more when the component (C) is 100 mass%. 如請求項1或2之樹脂組成物，其中，進一步包含(E)無機填充材。 The resin composition of claim 1 or 2, further comprising (E) an inorganic filler. 如請求項5之樹脂組成物，其中，將樹脂組成物中的不揮發成分設為100質量%時，(E)成分的含量為50質量%以上。 The resin composition of claim 5, wherein the content of component (E) is 50 mass% or more when the non-volatile components in the resin composition are 100 mass%. 如請求項1或2之樹脂組成物，其係絕緣層形成用。 For example, the resin composition of claim 1 or 2 is used for forming an insulating layer. 如請求項1或2之樹脂組成物，其係用來形成導體層的絕緣層形成用。 The resin composition according to claim 1 or 2 is used to form an insulating layer for forming a conductor layer. 如請求項1或2之樹脂組成物，其係用來以濺鍍或金屬箔來形成導體層的絕緣層形成用。 The resin composition of claim 1 or 2 is used to form an insulating layer for forming a conductor layer by sputtering or metal foil. 如請求項1或2之樹脂組成物，其係具有頂部孔徑為45μm以下的通孔的絕緣層形成用。 The resin composition of claim 1 or 2 is used for forming an insulating layer having a through hole with a top pore diameter of 45 μm or less. 如請求項1或2之樹脂組成物，其係厚度為20μm以下的絕緣層形成用。 The resin composition of claim 1 or 2 is used for forming an insulating layer with a thickness of 20 μm or less. 一種樹脂薄片，其特徵為包含：支撐體與設置於該支撐體上的樹脂組成物層，該樹脂組成物層包含請求項1~11中任一項之樹脂組成物。 A resin sheet, characterized by comprising: a support body and a resin composition layer provided on the support body, the resin composition layer containing the resin composition of any one of claims 1 to 11. 一種包含絕緣層的印刷配線板，其特徵為該絕緣層係藉由請求項1~11中任一項之樹脂組成物的硬化物所形成者。 A printed wiring board including an insulating layer, characterized in that the insulating layer is formed by a cured product of the resin composition in any one of claims 1 to 11. 一種半導體裝置，其特徵為包含請求項13之印刷配線板。 A semiconductor device characterized by including the printed wiring board of claim 13.
TW108125420A 2018-07-26 2019-07-18 resin composition TWI811399B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-140745 2018-07-26
JP2018140745A JP7099128B2 (en) 2018-07-26 2018-07-26 Resin composition

Publications (2)

Publication Number Publication Date
TW202012535A TW202012535A (en) 2020-04-01
TWI811399B true TWI811399B (en) 2023-08-11

Family

ID=69426935

Family Applications (1)

Application Number Title Priority Date Filing Date
TW108125420A TWI811399B (en) 2018-07-26 2019-07-18 resin composition

Country Status (4)

Country Link
JP (1) JP7099128B2 (en)
KR (1) KR20200012762A (en)
CN (1) CN110791130B (en)
TW (1) TWI811399B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7272473B2 (en) * 2018-07-26 2023-05-12 味の素株式会社 resin composition
WO2023167151A1 (en) * 2022-03-04 2023-09-07 旭化成株式会社 Block copolymer, resin composition, cured product, resin film, prepreg, multilayer body and material for electronic circuit boards
CN116693781A (en) 2022-03-04 2023-09-05 旭化成株式会社 Block copolymer, resin composition, cured product, resin film, prepreg, laminate, and material for electronic circuit board
JP2024021049A (en) 2022-08-02 2024-02-15 旭化成株式会社 Resin composition, cured product, resin film, prepreg, laminate, and material for electronic circuit substrates
JP2024021048A (en) 2022-08-02 2024-02-15 旭化成株式会社 Resin composition, cured product, resin film, prepreg, laminate, and material for electronic circuit substrates
JP2024021047A (en) 2022-08-02 2024-02-15 旭化成株式会社 Resin composition, cured product, resin film, prepreg, laminate, and material for electronic circuit substrates
JP2024059084A (en) 2022-10-17 2024-04-30 旭化成株式会社 Conjugated diene copolymer, resin composition, cured product, resin film, prepreg, laminate, and electronic circuit board material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008248141A (en) * 2007-03-30 2008-10-16 Nippon Steel Chem Co Ltd Flame retardant curable resin composition
CN106574110A (en) * 2014-10-22 2017-04-19 纳美仕有限公司 Resin composition, and insulating film and semiconductor device using same
CN108148349A (en) * 2016-12-02 2018-06-12 味之素株式会社 Resin combination
TW201936849A (en) * 2018-02-05 2019-09-16 日商迪睿合股份有限公司 Adhesive composition, thermosetting adhesive sheet and printed wiring board

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6570259B2 (en) 2015-02-11 2019-09-04 ナミックス株式会社 Resin composition, insulating film, and semiconductor device
JP7051333B2 (en) 2017-08-25 2022-04-11 日鉄ケミカル＆マテリアル株式会社 Curable resin composition, its cured product, curable composite material, metal leaf with resin, and varnish for circuit board material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008248141A (en) * 2007-03-30 2008-10-16 Nippon Steel Chem Co Ltd Flame retardant curable resin composition
CN106574110A (en) * 2014-10-22 2017-04-19 纳美仕有限公司 Resin composition, and insulating film and semiconductor device using same
CN108148349A (en) * 2016-12-02 2018-06-12 味之素株式会社 Resin combination
TW201936849A (en) * 2018-02-05 2019-09-16 日商迪睿合股份有限公司 Adhesive composition, thermosetting adhesive sheet and printed wiring board

Also Published As

Publication number Publication date
CN110791130A (en) 2020-02-14
KR20200012762A (en) 2020-02-05
JP7099128B2 (en) 2022-07-12
JP2020015861A (en) 2020-01-30
TW202012535A (en) 2020-04-01
CN110791130B (en) 2024-01-02

Similar Documents

Publication Publication Date Title
TWI811399B (en) resin composition
TWI815509B (en) resin composition
JP7020332B2 (en) Resin composition
TWI825222B (en) resin composition
JP7342348B2 (en) resin composition
JP2023002638A (en) resin composition
JP7287418B2 (en) resin composition
TWI820163B (en) resin composition
JP7459611B2 (en) Resin Sheet
TWI830727B (en) resin composition
TWI830735B (en) resin composition
JP7318699B2 (en) resin composition
KR20200104236A (en) Resin compositions
TWI811356B (en) resin composition
JP7298383B2 (en) Resin composition, cured product of resin composition, resin sheet, printed wiring board and semiconductor device
JP7272473B2 (en) resin composition
TW202146574A (en) Resin composition
JP7414143B2 (en) resin composition
JP2022184518A (en) resin sheet
TW202206523A (en) Resin composition capable of obtaining a cured product with low dielectric constant
KR20220025674A (en) Resin composition
JP2023124504A (en) resin composition
JP2021181557A (en) Resin composition