TW201704333A - Resin composition - Google Patents

Resin composition Download PDF

Info

Publication number
TW201704333A
TW201704333A TW105103846A TW105103846A TW201704333A TW 201704333 A TW201704333 A TW 201704333A TW 105103846 A TW105103846 A TW 105103846A TW 105103846 A TW105103846 A TW 105103846A TW 201704333 A TW201704333 A TW 201704333A
Authority
TW
Taiwan
Prior art keywords
resin composition
component
insulating layer
mass
layer
Prior art date
Application number
TW105103846A
Other languages
Chinese (zh)
Other versions
TWI696657B (en
Inventor
Tatsuya Homma
Hanae Tatsuhira
Original Assignee
Ajinomoto Kk
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 Ajinomoto Kk filed Critical Ajinomoto Kk
Publication of TW201704333A publication Critical patent/TW201704333A/en
Application granted granted Critical
Publication of TWI696657B publication Critical patent/TWI696657B/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • C08K3/28—Nitrogen-containing compounds
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/40—Mountings or securing means for detachable cooling or heating arrangements ; fixed by friction, plugs or springs
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48225—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Epoxy Resins (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)

Abstract

Provided is a resin composition which gives cured objects that exhibit sufficient heat-diffusing properties and have a satisfactory strength of adhesion to metal layers. The resin composition comprises (A) an epoxy resin, (B) a hardener, and (C) inorganic fillers, wherein the component (B) comprises a liquid phenolic hardener and the component (C) comprises an inorganic filler (C1) having an average particle diameter of 0.1 [mu]m or larger but smaller than 3 [mu]m, an inorganic filler (C2) having an average particle diameter of 3 [mu]m or larger but smaller than 10 [mu]m, and an inorganic filler (C3) having an average particle diameter of 10-35 [mu]m.

Description

樹脂組成物 Resin composition

本發明係關於樹脂組成物。進一步關於接著薄膜、印刷配線板、功率半導體裝置、及層合體。 The present invention relates to a resin composition. Further, the film, the printed wiring board, the power semiconductor device, and the laminate are bonded.

近年來，電子機器之小型化及高機能化進展，在印刷配線板之半導體元件的安裝密度有提高的傾向。伴隨安裝之半導體元件的高機能化，亦尋求有效率擴散半導體元件所產生的熱之技術。例如，專利文獻1中，揭示有使包含樹脂、與具有特定平均粒徑之無機填充材的高熱傳導性樹脂組成物硬化，以形成印刷配線板之絕緣層的技術。 In recent years, the miniaturization and high performance of electronic devices have progressed, and the mounting density of semiconductor elements in printed wiring boards tends to increase. With the high performance of the mounted semiconductor element, a technique for efficiently diffusing heat generated by the semiconductor element is also sought. For example, Patent Document 1 discloses a technique of curing a high thermal conductive resin composition containing a resin and an inorganic filler having a specific average particle diameter to form an insulating layer of a printed wiring board.

又專利文獻2中，揭示有應改善使用發熱量特別大之電力用半導體元件(亦稱為「功率半導體元件」)之半導體模組的放熱性，將該半導體模組藉由接著劑與金屬放熱板接著所得到之功率半導體裝置。 Further, Patent Document 2 discloses that the heat dissipation property of a semiconductor module using a power semiconductor element (also referred to as a "power semiconductor element") having a particularly large amount of heat generation is improved, and the semiconductor module is radiated by an adhesive and a metal. The board then proceeds to the resulting power semiconductor device.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2013-189625號公報 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2013-189625

[專利文獻2]日本特開2002-246542號公報 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2002-246542

本發明者們，為了更有效率使半導體元件所產生的熱擴散，針對絕緣層之熱擴散性進行研討。其結果，本發明者們發現使包含無機填充材之樹脂組成物硬化，以形成絕緣層的情況下，所得之絕緣層之熱擴散性與對於金屬層(導體層)之密著強度有權衡(Trade-off)關係。詳細而言，發現藉由提高樹脂組成物中之無機填充材的含量，雖可提昇所得之絕緣層之熱擴散性，但於表現充分之熱擴散性的程度提高無機填充材的含量時，所得之絕緣層對於金屬層(導體層)之密著強度不佳。即使絕緣層本身之熱擴散性提高，起因於絕緣層-金屬層間之密著不佳，絕緣層-金屬層間之熱擴散劣化的情況下，作為印刷配線板全體達成所期望熱擴散性是有困難的。 The inventors of the present invention have studied the thermal diffusivity of the insulating layer in order to more efficiently diffuse heat generated by the semiconductor element. As a result, the present inventors have found that when the resin composition containing the inorganic filler is cured to form an insulating layer, the thermal diffusivity of the obtained insulating layer is balanced with the adhesion strength to the metal layer (conductor layer) ( Trade-off) relationship. Specifically, it has been found that by increasing the content of the inorganic filler in the resin composition, the thermal diffusibility of the obtained insulating layer can be improved, but when the content of the inorganic filler is increased to the extent of exhibiting sufficient thermal diffusibility, The insulating layer has a poor adhesion strength to the metal layer (conductor layer). Even if the thermal diffusibility of the insulating layer itself is improved, the adhesion between the insulating layer and the metal layer is poor, and when the thermal diffusion between the insulating layer and the metal layer is deteriorated, it is difficult to achieve desired thermal diffusivity as the entire printed wiring board. of.

本發明之課題係提供一種帶來表現充分之熱擴散性，同時對於金屬層呈現良好之密著強度之硬化物的樹脂組成物。 An object of the present invention is to provide a resin composition which exhibits sufficient thermal diffusibility and exhibits a good adhesion strength to a metal layer.

本發明者們，針對上述之課題進行努力研究 的結果，發現藉由使用具有下述特定構成之樹脂組成物，可解決上述課題，而完成本發明。 The present inventors have made an effort to study the above problems. As a result, it has been found that the above problems can be solved by using a resin composition having the specific configuration described below, and the present invention has been completed.

亦即，本發明係包含以下之內容。 That is, the present invention includes the following contents.

[1]一種樹脂組成物，其係包含(A)環氧樹脂、(B)硬化劑及(C)無機填充材之樹脂組成物，(B)成分係包含液狀酚系硬化劑，(C)成分係包含(C1)平均粒徑0.1μm以上未滿3μm之無機填充材、(C2)平均粒徑3μm以上未滿10μm之無機填充材及(C3)平均粒徑10μm以上且35μm以下之無機填充材。 [1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) a resin composition of an inorganic filler, and (B) a component comprising a liquid phenolic curing agent, (C) The component contains (C1) an inorganic filler having an average particle diameter of 0.1 μm or more and less than 3 μm, (C2) an inorganic filler having an average particle diameter of 3 μm or more and less than 10 μm, and (C3) an inorganic material having an average particle diameter of 10 μm or more and 35 μm or less. Filling material.

[2]如[1]之樹脂組成物，其中，將(C)成分的含量定為100質量%的情況下，(C1)成分的含量為5質量%~40質量%、(C2)成分的含量為5質量%~40質量%、(C3)成分的含量為20質量%~90質量%。 [2] The resin composition according to [1], wherein, when the content of the component (C) is 100% by mass, the content of the component (C1) is 5% by mass to 40% by mass, and the component (C2) The content is 5% by mass to 40% by mass, and the content of the component (C3) is 20% by mass to 90% by mass.

[3]如[1]或[2]之樹脂組成物，其中，將(C1)成分之平均粒徑定為dc1(μm)，將(C2)成分之平均粒徑定為dc2(μm)，將(C3)成分之平均粒徑定為dc3(μm)時，dc1、dc2及dc3係滿足dc2-dc1≧0.5及dc3-dc2≧5.0的關係。 [3] The resin composition according to [1] or [2], wherein the average particle diameter of the component (C1) is d c1 (μm), and the average particle diameter of the component (C2) is d c2 (μm) When the average particle diameter of the component (C3) is d c3 (μm), d c1 , d c2 and d c3 satisfy the relationship of d c2 - d c1 ≧ 0.5 and d c3 - d c2 ≧ 5.0.

[4]如[1]~[3]中任一項之樹脂組成物，其中，將樹脂組成物中之不揮發成分定為100體積%的情況下，(C)成分的含量為60體積%~90體積%。 [4] The resin composition according to any one of [1] to [3] wherein, in the case where the nonvolatile content in the resin composition is 100% by volume, the content of the component (C) is 60% by volume. ~90% by volume.

[5]如[1]~[4]中任一項之樹脂組成物，其中，(C)成分係包含熱傳導率25W/m．K以上之無機填充材。 [5] The resin composition according to any one of [1] to [4] wherein the component (C) comprises a thermal conductivity of 25 W/m. An inorganic filler of K or more.

[6]如[1]~[5]中任一項之樹脂組成物，其中，(C)成分係包含選自由氮化鋁、氧化鋁、氮化硼、氮化矽及碳化矽所構成之群組中之1或2以上的無機填充材。 [6] The resin composition according to any one of [1] to [5] wherein the component (C) comprises a material selected from the group consisting of aluminum nitride, aluminum oxide, boron nitride, tantalum nitride, and tantalum carbide. One or more inorganic fillers in the group.

[7]如[1]~[6]中任一項之樹脂組成物，其中，(C)成分係包含氮化鋁。 [7] The resin composition according to any one of [1] to [6] wherein the component (C) comprises aluminum nitride.

[8]如[1]~[7]中任一項之樹脂組成物，其中，(A)成分係包含液狀環氧樹脂。 [8] The resin composition according to any one of [1] to [7] wherein the component (A) comprises a liquid epoxy resin.

[9]如[1]~[8]中任一項之樹脂組成物，其係進一步包含(D)硬化促進劑。 [9] The resin composition according to any one of [1] to [8] further comprising (D) a hardening accelerator.

[10]如[9]之樹脂組成物，其中，(D)成分係包含四取代鏻鹽。 [10] The resin composition according to [9], wherein the component (D) comprises a tetra-substituted phosphonium salt.

[11]如[1]~[10]中任一項之樹脂組成物，其係進一步包含(E)碳二醯亞胺化合物。 [11] The resin composition according to any one of [1] to [10] further comprising (E) a carbodiimide compound.

[12]一種接著薄膜，其係包含支持體、與樹脂組成物層，該樹脂組成物層係由與該支持體接合之如[1]~[11]中任一項之樹脂組成物所構成。 [12] A contiguous film comprising a support and a resin composition layer, the resin composition layer being composed of a resin composition according to any one of [1] to [11] bonded to the support. .

[13]如[12]之接著薄膜，其中，樹脂組成物層之最低熔融黏度為500泊~20000泊。 [13] The film according to [12], wherein the resin composition layer has a minimum melt viscosity of 500 poise to 20,000 poise.

[14]如[12]或[13]之接著薄膜，其中，將(C3)成分之平均粒徑定為dc3(μm)時，樹脂組成物層之厚度為(dc3+45)μm~200μm。 [14] The film of [12] or [13], wherein the thickness of the resin composition layer is (d c3 + 45) μm when the average particle diameter of the component (C3) is d c3 (μm). 200 μm.

[15]如[12]~[14]中任一項之接著薄膜，其係高熱傳導用。 [15] The adhesive film according to any one of [12] to [14] which is used for high heat conduction.

[16]如[12]~[15]中任一項之接著薄膜，其係使用在 金屬放熱體與半導體模組的接著。 [16] The adhesive film according to any one of [12] to [15], which is used in The metal heat sink is followed by the semiconductor module.

[17]一種印刷配線板，其係包含藉由如[1]~[11]中任一項之樹脂組成物的硬化物所形成之絕緣層。 [17] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [11].

[18]一種功率半導體裝置，其係包含具有第1及第2主面之金屬放熱體、具有第1及第2主面之半導體模組、及絕緣層，該絕緣層係以金屬放熱體之第1主面與半導體模組之第2主面進行接合的方式，藉由設置於金屬放熱體與半導體模組之間的如[1]~[11]中任一項之樹脂組成物的硬化物形成。 [18] A power semiconductor device comprising a metal heat radiator having first and second main faces, a semiconductor module having first and second main faces, and an insulating layer, wherein the insulating layer is a metal heat releasing body; The first main surface is bonded to the second main surface of the semiconductor module, and the resin composition of any one of [1] to [11] provided between the metal heat radiator and the semiconductor module is hardened. Object formation.

[19]如[18]之功率半導體裝置，其中，金屬放熱體之第1主面及半導體模組之第2主面之至少一者的算術平均粗糙度(Ra)為500nm以下。 [19] The power semiconductor device according to [18], wherein the arithmetic mean roughness (Ra) of at least one of the first main surface of the metal heat radiator and the second main surface of the semiconductor module is 500 nm or less.

[20]如[18]或[19]之功率半導體裝置，其中，絕緣層之熱傳導率為8W/m．K以上，絕緣層與金屬放熱體之第1主面及半導體模組之第2主面之至少一者的密著強度為0.5kgf/cm以上。 [20] The power semiconductor device according to [18] or [19], wherein the thermal conductivity of the insulating layer is 8 W/m. K or more, the adhesion strength between the insulating layer and at least one of the first main surface of the metal heat radiator and the second main surface of the semiconductor module is 0.5 kgf/cm or more.

[21]一種層合體，其係絕緣層與金屬層之層合體，絕緣層之熱傳導率為8W/m．K以上，且絕緣層與金屬層的密著強度為0.5kgf/cm以上。 [21] A laminate, which is a laminate of an insulating layer and a metal layer, and the thermal conductivity of the insulating layer is 8 W/m. K or more, and the adhesion strength between the insulating layer and the metal layer is 0.5 kgf/cm or more.

[22]如[21]之層合體，其中，與金屬層之絕緣層接合之表面的算術平均粗糙度(Ra)為500nm以下。 [22] The laminate according to [21], wherein the surface to be bonded to the insulating layer of the metal layer has an arithmetic mean roughness (Ra) of 500 nm or less.

[23]如[21]或[22]之層合體，其中，金屬層係由銅或鋁所構成。 [23] The laminate of [21] or [22] wherein the metal layer is composed of copper or aluminum.

[24]如[21]~[23]中任一項之層合體，其中，絕緣層係藉由如[1]~[11]中任一項之樹脂組成物的硬化物形成而成。 [24] The laminate of any one of [21] to [23], wherein the insulating layer is formed by a cured product of the resin composition according to any one of [1] to [11].

根據本發明，可提供一種帶來表現充分之熱擴散性，同時對於金屬層呈現良好之密著強度之硬化物的樹脂組成物。 According to the present invention, it is possible to provide a resin composition which exhibits sufficient heat diffusibility while exhibiting a good adhesion strength to a metal layer.

藉由使用本發明之樹脂組成物，形成印刷配線板之絕緣層，可有效率擴散半導體元件所產生的熱。 By using the resin composition of the present invention, an insulating layer of a printed wiring board is formed, and heat generated by the semiconductor element can be efficiently diffused.

本發明之樹脂組成物由於提供熱擴散性及對於金屬層之密著強度雙方優異之硬化物，在功率半導體裝置作為用以使半導體模組與金屬放熱體接著之接著劑係極為有用。 The resin composition of the present invention is useful as a cured product which is excellent in both thermal diffusibility and adhesion strength to a metal layer, and is used as a bonding agent for a semiconductor module and a metal heat radiator.

1‧‧‧金屬放熱體 1‧‧‧ metal radiator

1a‧‧‧金屬放熱體之第1主面 1a‧‧‧1st main face of metal radiator

1b‧‧‧金屬放熱體之第2主面 1b‧‧‧2nd main face of metal radiator

2‧‧‧絕緣層 2‧‧‧Insulation

3‧‧‧半導體模組 3‧‧‧Semiconductor Module

3b‧‧‧半導體模組之第2主面 3b‧‧‧2nd main surface of the semiconductor module

4‧‧‧半導體元件基板 4‧‧‧Semiconductor component substrate

5‧‧‧金屬層(電路) 5‧‧‧metal layer (circuit)

6‧‧‧基板 6‧‧‧Substrate

7‧‧‧金屬層 7‧‧‧metal layer

8‧‧‧半導體元件 8‧‧‧Semiconductor components

9‧‧‧導線 9‧‧‧Wire

10‧‧‧功率半導體裝置 10‧‧‧Power semiconductor devices

[圖1]圖1係表示本發明之功率半導體裝置之模式圖。 Fig. 1 is a schematic view showing a power semiconductor device of the present invention.

以下，將本發明按照其適合之實施形態進行詳細說明。 Hereinafter, the present invention will be described in detail in accordance with suitable embodiments thereof.

[樹脂組成物] [Resin composition]

本發明之樹脂組成物，其特徵為包含(A)環氧樹脂、(B)硬化劑及(C)無機填充材，(B)成分係包含液狀酚系硬化劑，(C)成分係包含(C1)平均粒徑0.1μm以上未滿3μm之無機填充材、(C2)平均粒徑3μm以上未滿10μm之無機填充材及(C3)平均粒徑10μm以上且35μm以下之無機填充材。 The resin composition of the present invention is characterized by comprising (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, (B) a component comprising a liquid phenolic curing agent, and (C) a component comprising (C1) an inorganic filler having an average particle diameter of 0.1 μm or more and less than 3 μm, (C2) an inorganic filler having an average particle diameter of 3 μm or more and less than 10 μm, and (C3) an inorganic filler having an average particle diameter of 10 μm or more and 35 μm or less.

如先述，使包含無機填充材之樹脂組成物硬化，以形成絕緣層的情況下，所得之絕緣層之熱擴散性，係與對於金屬層(導體層)之密著強度有權衡關係。對此，包含組合上述特定之(A)~(C)成分之本發明的樹脂組成物，可實現熱擴散性與對於金屬層之密著強度雙方皆優異之硬化物(絕緣層)。 As described above, when the resin composition containing the inorganic filler is cured to form an insulating layer, the thermal diffusivity of the obtained insulating layer is in a weighted relationship with the adhesion strength to the metal layer (conductor layer). On the other hand, the resin composition of the present invention containing the specific components (A) to (C) described above can achieve a cured product (insulating layer) excellent in both thermal diffusibility and adhesion strength to the metal layer.

<(A)環氧樹脂> <(A) Epoxy Resin>

作為環氧樹脂，例如可列舉雙酚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、參酚型環氧樹脂、萘酚酚醛清漆型環氧樹脂、酚酚醛清漆型環氧樹脂、tert-丁基-鄰苯二酚型環氧樹脂、萘型環氧樹脂、萘酚型環氧樹脂、蔥型環氧樹脂、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、具有丁二烯結構之環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂、含有螺環之環氧樹脂、環己烷 二甲醇型環氧樹脂、伸萘基醚型環氧樹脂、三羥甲基型環氧樹脂、四苯基乙烷型環氧樹脂等。環氧樹脂可1種單獨使用，亦可組合2種以上使用。 Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, and ginseng. Phenolic epoxy resin, naphthol novolak epoxy resin, phenol novolak epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, Onion type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, butadiene Structure epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane Dimethanol type epoxy resin, —naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, and the like. Epoxy resins may be used alone or in combination of two or more.

環氧樹脂，較佳為包含於1分子中具有2個以上環氧基之環氧樹脂。將環氧樹脂之不揮發成分定為100質量%時，較佳為至少50質量%以上為於1分子中具有2個以上環氧基之環氧樹脂。 The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile content of the epoxy resin is 100% by mass, it is preferably at least 50% by mass or more of an epoxy resin having two or more epoxy groups in one molecule.

從具有充分之可撓性且得到操作性優異之接著薄膜的觀點，得到對於金屬層呈現良好之密著強度的樹脂組成物層(也就是絕緣層)的觀點來看，環氧樹脂較佳為包含於溫度20℃為液狀之環氧樹脂(以下稱為「液狀環氧樹脂」)。作為液狀環氧樹脂，較佳為於1分子中具有2個以上環氧基之液狀環氧樹脂，更佳為於1分子中具有2個以上環氧基之芳香族系液狀環氧樹脂。在本發明，所謂芳香族系之環氧樹脂，係指於其分子內具有芳香環之環氧樹脂。 From the viewpoint of obtaining a resin composition layer (that is, an insulating layer) which exhibits good adhesion strength to a metal layer from the viewpoint of having sufficient flexibility and excellent handleability, the epoxy resin is preferably It is contained in a liquid epoxy resin (hereinafter referred to as "liquid epoxy resin") at a temperature of 20 °C. The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, more preferably an aromatic liquid epoxy having two or more epoxy groups in one molecule. Resin. In the present invention, the aromatic epoxy resin refers to an epoxy resin having an aromatic ring in its molecule.

環氧樹脂可包含於溫度20℃為固體狀之環氧樹脂(亦稱為「固體狀環氧樹脂」)。作為固體狀環氧樹脂，較佳為於1分子中具有3個以上環氧基之固體狀環氧樹脂，更佳為於1分子中具有3個以上環氧基之芳香族系固體狀環氧樹脂。 The epoxy resin may be an epoxy resin (also referred to as "solid epoxy resin") which is solid at a temperature of 20 ° C. The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, more preferably an aromatic solid epoxy having three or more epoxy groups in one molecule. Resin.

尚，在本發明，於溫度20℃是液狀或固體狀的區別，係以對象成分有單獨狀態(亦即，實質上未包含溶劑等之其他成分的狀態)時來進行。 Further, in the present invention, the difference between the liquid state and the solid state at a temperature of 20 ° C is performed when the target component has a single state (that is, a state in which substantially no other component such as a solvent is contained).

作為環氧樹脂，併用液狀環氧樹脂與固體狀環氧樹脂的情況下，該等之量比(液狀環氧樹脂：固體狀環氧樹脂)以質量比為1：0.1~1：4的範圍較佳，更佳為1：0.3~1：3之範圍，再更佳為1：0.5~1：2.5之範圍，特佳為1：0.7~1：2的範圍。藉由將液狀環氧樹脂與固體狀環氧樹脂的量比定為該範圍，即使於無機填充材含量高的情況下，亦可得到呈現良好之機械強度，同時對於金屬層呈現充分之密著強度的絕緣層。 In the case of an epoxy resin and a liquid epoxy resin and a solid epoxy resin, the mass ratio (liquid epoxy resin: solid epoxy resin) is 1:0.1 to 1:4 by mass ratio. The range is preferably from 1:0.3 to 1:3, more preferably from 1:0.5 to 1:2.5, and particularly preferably from 1:0.7 to 1:2. By setting the ratio of the amount of the liquid epoxy resin to the solid epoxy resin to be in this range, even when the content of the inorganic filler is high, good mechanical strength can be obtained, and at the same time, the metal layer is sufficiently dense. Insulation of strength.

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、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、酚酚醛清漆型環氧樹脂、2官能脂肪族環氧樹脂、環己烷二甲醇型環氧樹脂及具有丁二烯結構之環氧樹脂，更佳為雙酚A型環氧樹脂、雙酚F型環氧樹脂、2官能脂肪族環氧樹脂及萘型環氧樹脂。作為液狀環氧樹脂之具體例，可列舉DIC(股)製之「HP4032」、「HP4032H」、「HP4032D」、「HP4032SS」(萘型環氧樹脂)、三菱化學(股)製之「jER828EL」、「828US」(雙酚A型環氧樹脂)、「jER807」(雙酚F型環氧樹脂)、「jER152」(酚酚醛清漆型環氧樹脂)、「YL7410」(2官能脂肪族環氧樹脂)、新日鐵住金化學(股)製之「ZX1059」(雙酚A型環氧樹脂與雙酚F型環氧樹脂之混合品)、Nagase Chemte X(股)製之「EX-721」(縮水甘油酯型環氧樹脂)、(股)Daicel製之「CELLOXIDE 2021P」(具有酯 骨架之脂環式環氧樹脂)、「PB-3600」(具有丁二烯結構之環氧樹脂)。此等可1種單獨使用，亦可組合2種以上使用。 As the liquid epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin, a phenol novolac is preferable. Varnish type epoxy resin, 2-functional aliphatic epoxy resin, cyclohexane dimethanol type epoxy resin and epoxy resin having butadiene structure, more preferably bisphenol A type epoxy resin, bisphenol F type ring An oxygen resin, a bifunctional aliphatic epoxy resin, and a naphthalene epoxy resin. Specific examples of the liquid epoxy resin include "HP4032", "HP4032H", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Co., Ltd., and "jER828EL" manufactured by Mitsubishi Chemical Corporation. "828US" (bisphenol A epoxy resin), "jER807" (bisphenol F epoxy resin), "jER152" (phenol novolak epoxy resin), "YL7410" (2-functional aliphatic ring) "Oxygen resin", "ZX1059" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin), and "EX-721" manufactured by Nagase Chemte X Co., Ltd. (Glycidyl Ester Resin), "CELLOXIDE 2021P" made by Daicel (with ester) Skeleton alicyclic epoxy resin), "PB-3600" (epoxy resin with butadiene structure). These may be used alone or in combination of two or more.

作為固體狀環氧樹脂，較佳為萘型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、參酚型環氧樹脂、萘酚型環氧樹脂、聯苯型環氧樹脂、伸萘基醚型環氧樹脂、蔥型環氧樹脂、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，更佳為萘型4官能環氧樹脂、萘酚型環氧樹脂、聯苯型環氧樹脂、雙環戊二烯型環氧樹脂、及雙酚AF型環氧樹脂。作為固體狀環氧樹脂之具體例，可列舉DIC(股)製之「HP-4700」、「HP-4710」(萘型4官能環氧樹脂)、「N-690」、「N-695」(甲酚酚醛清漆型環氧樹脂)、「HP7200」、「HP7200H」、「HP7200HH」(雙環戊二烯型環氧樹脂)、「EXA7311」、「EXA7311-G3」、「EXA7311-G4」、「EXA7311-G4S」、「HP6000」(伸萘基醚型環氧樹脂)、日本化藥(股)製之「EPPN-502H」(參酚型環氧樹脂)、「NC7000L」(萘酚酚醛清漆型環氧樹脂)、「NC3000H」、「NC3000」、「NC3000L」、「NC3100」(聯苯型環氧樹脂)、新日鐵住金化學(股)製之「ESN475V」(萘酚型環氧樹脂)、「ESN485」(萘酚酚醛清漆型環氧樹脂)、三菱化學(股)製之「YX4000H」、「YL6121」(聯苯型環氧樹脂)、「YX4000HK」(聯二甲苯醇(bixylenol)型環氧 樹脂)、「YX8800」(蔥型環氧樹脂)、大阪氣體化學(股)製之「PG-100」、「CG-500」、三菱化學(股)製之「YL7800」(茀型環氧樹脂)、三菱化學(股)製之「jER1010」(固體狀雙酚A型環氧樹脂)、「YL7723」、「YL7760」(雙酚AF型環氧樹脂)、「jER1031S」(四苯基乙烷型環氧樹脂)等。此等可1種單獨使用，亦可組合2種以上使用。 The solid epoxy resin is preferably a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a phenol type epoxy resin, or a naphthol type epoxy resin. Biphenyl type epoxy resin, naphthyl ether type epoxy resin, onion type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin, preferably It is a naphthalene type tetrafunctional epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a dicyclopentadiene type epoxy resin, and a bisphenol AF type epoxy resin. Specific examples of the solid epoxy resin include "HP-4700" manufactured by DIC Co., Ltd., "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690", and "N-695". (cresol novolac type epoxy resin), "HP7200", "HP7200H", "HP7200HH" (dicyclopentadiene type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", " "EXA7311-G4S", "HP6000" (streptyl ether type epoxy resin), "EPPN-502H" ("phenol type epoxy resin", "NC7000L" made by Nippon Kayaku Co., Ltd. (naphthol novolac type) Epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. "ESN485" (naphthol novolak type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type) Epoxy "Resin", "YX8800" (onion type epoxy resin), "PG-100" made by Osaka Gas Chemical Co., Ltd., "CG-500", and "YL7800" made by Mitsubishi Chemical Corporation ), "jER1010" (solid bisphenol A type epoxy resin), "YL7723", "YL7760" (bisphenol AF type epoxy resin), "jER1031S" (tetraphenyl ethane) manufactured by Mitsubishi Chemical Corporation Type epoxy resin). These may be used alone or in combination of two or more.

樹脂組成物中之環氧樹脂的含量較佳為2質量%以上，更佳為3質量%以上，再更佳為4質量%以上或5質量%以上。環氧樹脂的含量之上限雖並未特別限定，但較佳為60質量%以下，更佳為55質量%以下，再更佳為50質量%以下，45質量%以下、40質量%以下、35質量%以下、或30質量%以下。 The content of the epoxy resin in the resin composition is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more or 5% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited, but is preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, 45% by mass or less, or 40% by mass or less, and 35 parts by weight. The mass% or less, or 30% by mass or less.

尚，在本發明，構成樹脂組成物之各成分的含量，除非另有明文規定，係將樹脂組成物中之不揮發成分定為100質量%時之值。 In the present invention, the content of each component constituting the resin composition is a value obtained by setting the nonvolatile content in the resin composition to 100% by mass unless otherwise specified.

環氧樹脂之環氧當量較佳為50~5000，更佳為50~3000，再更佳為80~2000，又再更佳為110~1000。藉由成為此範圍，可提供硬化物之交聯密度變充分且表面粗糙度小之絕緣層。尚，環氧當量可依JIS K7236測定，係包含1當量之環氧基之樹脂的質量。 The epoxy equivalent of the epoxy resin is preferably from 50 to 5,000, more preferably from 50 to 3,000, still more preferably from 80 to 2,000, still more preferably from 110 to 1,000. By setting it as such a range, it is possible to provide an insulating layer in which the crosslinking density of the cured product is sufficient and the surface roughness is small. Further, the epoxy equivalent can be measured in accordance with JIS K7236, which is the mass of a resin containing 1 equivalent of an epoxy group.

環氧樹脂之重量平均分子量較佳為100~5000，更佳為250~3000，再更佳為400~1500。於此，環氧樹脂之重量平均分子量係藉由凝膠滲透層析(GPC) 法所測定之聚苯乙烯換算之重量平均分子量。 The weight average molecular weight of the epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, still more preferably from 400 to 1,500. Here, the weight average molecular weight of the epoxy resin is by gel permeation chromatography (GPC). The weight average molecular weight in terms of polystyrene measured by the method.

<(B)硬化劑> <(B) hardener>

在本發明之樹脂組成物，其特徵為硬化劑係包含液狀酚系硬化劑。藉由包含液狀酚系硬化劑，即使於無機填充材含量高的情況下，亦可實現對於金屬層呈現充分之密著強度的絕緣層。尚，在本發明，所謂液狀酚系硬化劑，係指於溫度20℃為液狀之酚系硬化劑。 The resin composition of the present invention is characterized in that the curing agent contains a liquid phenol-based curing agent. By including a liquid phenol-based curing agent, even when the content of the inorganic filler is high, an insulating layer exhibiting sufficient adhesion strength to the metal layer can be realized. In the present invention, the liquid phenolic curing agent refers to a phenolic curing agent which is liquid at a temperature of 20 ° C.

作為可適合使用在本發明之樹脂組成物的液狀酚系硬化劑，例如可列舉液狀烷基酚樹脂、液狀烯丙基酚樹脂。其中，在(A)成分及(C)成分的組合，從得到熱擴散性及對於金屬層之密著強度雙方更為優異之絕緣層的觀點來看，作為液狀酚系硬化劑，較佳為液狀烷基酚樹脂。 The liquid phenolic curing agent which can be suitably used in the resin composition of the present invention is, for example, a liquid alkylphenol resin or a liquid allyl phenol resin. In particular, the combination of the component (A) and the component (C) is preferably a liquid phenol-based curing agent from the viewpoint of obtaining an insulating layer which is more excellent in thermal diffusibility and adhesion strength to the metal layer. It is a liquid alkylphenol resin.

液狀酚系硬化劑之酚性羥基當量，從得到對於金屬層呈現良好之密著強度的絕緣層的觀點來看，較佳為50~1000，更佳為70~800，再更佳為90~600。該酚性羥基當量係包含1當量酚性羥基之樹脂的質量。 The phenolic hydroxyl group equivalent of the liquid phenol-based curing agent is preferably from 50 to 1,000, more preferably from 70 to 1,000, still more preferably from the viewpoint of obtaining an insulating layer which exhibits good adhesion strength to the metal layer. ~600. The phenolic hydroxyl equivalent is a mass of a resin containing one equivalent of a phenolic hydroxyl group.

液狀酚系硬化劑之重量平均分子量較佳為100~4500，更佳為200~4000，再更佳為300~3000。液狀酚系硬化劑之重量平均分子量係藉由GPC法所測定之聚苯乙烯換算之重量平均分子量。 The weight average molecular weight of the liquid phenol-based hardener is preferably from 100 to 4,500, more preferably from 200 to 4,000, still more preferably from 300 to 3,000. The weight average molecular weight of the liquid phenol-based curing agent is a polystyrene-equivalent weight average molecular weight measured by a GPC method.

作為液狀酚系硬化劑之具體例，可列舉式(1)表示之液狀酚。 Specific examples of the liquid phenol-based curing agent include liquid phenol represented by the formula (1).

(式中，R1分別獨立表示氫原子、烷基、或烯基，R2及R3分別獨立表示氫原子或烷基，j係表示0~5之整數，複數之R1~R3可為同一亦可為相異)。 (wherein R 1 each independently represents a hydrogen atom, an alkyl group or an alkenyl group, R 2 and R 3 each independently represent a hydrogen atom or an alkyl group, j is an integer of 0 to 5, and plural R 1 to R 3 may be used. For the same, it can be different.)

烯基之碳原子數較佳為2~10，更佳為2~6，再更佳為2~4，特佳為3。其中，作為烯基，較佳為2-丙烯基(烯丙基)。 The number of carbon atoms of the alkenyl group is preferably 2 to 10, more preferably 2 to 6, more preferably 2 to 4, and particularly preferably 3. Among them, as the alkenyl group, a 2-propenyl group (allyl) is preferred.

烷基之碳原子數較佳為1~20，更佳為1~10，更佳為1~6，再更佳為1~4、1~3、或1。 The number of carbon atoms of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 6, more preferably from 1 to 4, from 1 to 3, or 1.

式(1)中，較佳為R1之至少一個為烷基、或烯基。式(1)中之烷基或烯基之個數，較佳為1以上。更佳為相對於式(1)中之1個苯環包含1個或2個烷基及/或烯基，再更佳為相對於式(1)中之1個苯環包含1個烷基及/或烯基。 In the formula (1), at least one of R 1 is preferably an alkyl group or an alkenyl group. The number of the alkyl group or the alkenyl group in the formula (1) is preferably 1 or more. More preferably, it contains 1 or 2 alkyl groups and/or alkenyl groups with respect to one benzene ring in the formula (1), and more preferably contains 1 alkyl group with respect to one benzene ring in the formula (1). And / or alkenyl.

此等當中，以R1係表示氫原子、或烯基較佳，以表示氫原子、或烯丙基更佳。又，以R2及R3係表示氫原子較佳。 Among these, a hydrogen atom or an alkenyl group is preferably represented by R 1 to further represent a hydrogen atom or an allyl group. And to R 2 and R 3 represents a hydrogen atom preferred system.

式(1)中，複數之R1可彼此為同一亦可為相異。對於R2~R3亦相同。 In the formula (1), the plural R 1 's may be the same or different from each other. The same applies to R 2 to R 3 .

式(1)中，j係表示0~5之整數，較佳為表示0~3之整數，更佳為表示0或1，再更佳為0。 In the formula (1), j is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1, more preferably 0.

作為液狀酚系硬化劑，例如可使用群榮化學工業(股)製之「ACG-1」、「APG-1」、「ELP-30」、「ELC」、明和化成(股)製之「MEH-8000」。 As the liquid phenol-based curing agent, for example, "ACG-1", "APG-1", "ELP-30", "ELC", and Mingwa Chemical Co., Ltd., manufactured by Kyoei Chemical Industry Co., Ltd., can be used. MEH-8000".

在本發明之樹脂組成物，(B)硬化劑除了液狀酚系硬化劑之外，亦可包含其他硬化劑。作為該其他硬化劑，只要是具有硬化環氧樹脂之機能則並未特別限定，例如可列舉固體狀酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑、苯并噁嗪系硬化劑、及氰酸酯酯系硬化劑。其他硬化劑可1種單獨使用，亦可組合2種以上使用。尚，在本發明，所謂固體狀酚系硬化劑，係指於溫度20℃為固體狀之酚系硬化劑。 In the resin composition of the present invention, the (B) curing agent may contain other curing agents in addition to the liquid phenolic curing agent. The other curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and examples thereof include a solid phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a benzoxazine-based curing agent. And cyanate ester-based hardeners. The other curing agents may be used alone or in combination of two or more. In the present invention, the solid phenolic curing agent refers to a phenolic curing agent which is solid at a temperature of 20 °C.

作為固體狀酚系硬化劑及萘酚系硬化劑，從耐熱性及耐水性的觀點來看，較佳為具有酚醛清漆結構之酚系硬化劑、或具有酚醛清漆結構之萘酚系硬化劑。又，從與金屬層的密著強度的觀點來看，較佳為含氮酚系硬化劑或含氮萘酚系硬化劑，更佳為含有三嗪結構之酚系硬化劑或含有三嗪結構之萘酚系硬化劑。其中，從耐熱性、耐水性、及高度滿足與導體層的密著強度的觀點來看，較佳為含有三嗪結構與酚醛清漆結構雙方之酚系硬化劑或萘酚系硬化劑。此等可1種單獨使用，亦可組合2種以上使用。作為固體狀酚系硬化劑及萘酚系硬化劑之市售品，例如可列舉明和化成(股)製之「MEH-7700」、「MEH-7810」、「MEH-7851」、日本化藥(股)製之「NHN」、「CBN」、「GPH」、新日鐵住金化學(股) 製之「SN-170」、「SN-180」、「SN-190」、「SN-475」、「SN-485」、「SN-495」、「SN-375」、「SN-395」、DIC(股)製之「LA-7052」、「LA-7054」、「LA-3018」、「LA-1356」、「TD2090」等。 The solid phenolic curing agent and the naphthol-based curing agent are preferably a phenolic curing agent having a novolak structure or a naphthol-based curing agent having a novolac structure from the viewpoint of heat resistance and water resistance. Moreover, from the viewpoint of the adhesion strength to the metal layer, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferred, and a benzene-based curing agent containing a triazine structure or a triazine-containing structure is more preferred. Naphthol-based hardener. Among them, from the viewpoint of heat resistance, water resistance, and high adhesion strength to the conductor layer, a phenol-based curing agent or a naphthol-based curing agent containing both a triazine structure and a novolac structure is preferable. These may be used alone or in combination of two or more. For example, "MEH-7700", "MEH-7810", "MEH-7851", and Nippon Chemical Co., Ltd., which are manufactured by Megumi Kasei Co., Ltd., are commercially available as a solid phenolic curing agent and a naphthol-based curing agent. "NHN", "CBN", "GPH", and Nippon Steel & Sumitomo Chemical Co., Ltd. "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-1356", "TD2090", etc. of DIC (share) system.

作為活性酯系硬化劑，雖並未特別限制，但一般而言較佳係使用於1分子中具有2個以上酚酯類、硫酚酯類、N-羥基胺酯類、雜環羥基化合物之酯類等之反應活性高之酯基的化合物。該活性酯系硬化劑較佳為藉由羧酸化合物及/或硫羧酸化合物與羥基化合物及/或硫醇化合物的縮合反應所得到者。特別是從耐熱性提昇的觀點來看，較佳為從羧酸化合物與羥基化合物所得之活性酯系硬化劑，更佳為從羧酸化合物與酚化合物及/或萘酚化合物所得之活性酯系硬化劑。作為羧酸化合物，例如可列舉苯甲酸、乙酸、琥珀酸、馬來酸、衣康酸、苯二甲酸、間苯二甲酸、對苯二甲酸、苯均四酸等。作為酚化合物或萘酚化合物，例如可列舉對苯二酚、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞(Phenolphthalein)、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、酚、o-甲酚、m-甲酚、p-甲酚、鄰苯二酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、間苯三酚、苯三醇、雙環戊二烯型二酚化合物、酚酚醛清漆等。於此，所謂「雙環戊二烯型二酚化合物」，係指於雙環戊二烯1分子縮合酚2分子所得之二酚化合物。具體而言，較佳為包含雙環戊二烯型二 酚結構之活性酯化合物、包含萘結構之活性酯化合物、包含酚酚醛清漆之乙醯基化物之活性酯化合物、包含酚酚醛清漆之苯甲醯基化物之活性酯化合物，其中更佳為包含萘結構之活性酯化合物、包含雙環戊二烯型二酚結構之活性酯化合物。此等可1種單獨使用，亦可組合2種以上使用。尚，所謂「雙環戊二烯型二酚結構」，係表示由伸苯基-雙環伸戊基-伸苯基所構成之2價結構單位。作為活性酯系硬化劑之市售品，作為包含雙環戊二烯型二酚結構之活性酯化合物，可列舉「EXB9451」、「EXB9460」、「EXB9460S」、「HPC8000-65T」(DIC(股)製)，作為包含萘結構之活性酯化合物，可列舉「EXB9416-70BK」(DIC(股)製)，作為包含酚酚醛清漆之乙醯基化物之活性酯化合物，可列舉「DC808」(三菱化學(股)製)，作為包含酚酚醛清漆之苯甲醯基化物之活性酯化合物，可列舉「YLH1026」(三菱化學(股)製)等。 The active ester-based curing agent is not particularly limited, but is generally preferably used in one molecule of two or more phenolic esters, thiophenolic esters, N-hydroxylamine esters, and heterocyclic hydroxy compounds. An ester group-based compound having a high reactivity such as an ester. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a sulfuric acid compound with a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of heat resistance improvement, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester system obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. hardener. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or the naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, and methylated bisphenol. F, methyl, bisphenol S, phenol, o- cresol, m- cresol, p-cresol, catechol, α - naphthol, [beta] naphthol, 1,5-dihydroxynaphthalene, 1 ,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene Diphenol compounds, phenol novolacs, and the like. Here, the "dicyclopentadiene type diphenol compound" means a diphenol compound obtained by condensing a phenol 2 molecule with a molecule of dicyclopentadiene. Specifically, it is preferably an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated phenolic novolac, and a benzophenone containing phenol novolac. An active ester compound of a mercapto compound, more preferably an active ester compound containing a naphthalene structure or an active ester compound containing a dicyclopentadiene type diphenol structure. These may be used alone or in combination of two or more. Further, the "dicyclopentadiene type diphenol structure" means a divalent structural unit composed of a phenyl-bicyclopentyl-phenylene group. As a commercial product of the active ester-based curing agent, examples of the active ester compound containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", and "HPC8000-65T" (DIC). "EXB9416-70BK" (manufactured by DIC Co., Ltd.), and an active ester compound containing an acetylation of a phenol novolak, "DC808" (Mitsubishi Chemical Co., Ltd.) (manufactured by Mitsubishi Chemical Co., Ltd.), etc., as an active ester compound containing a benzamidine phenolic phenolic varnish, "YLH1026" (manufactured by Mitsubishi Chemical Corporation).

作為苯并噁嗪系硬化劑之市售品，例如可列舉昭和高分子(股)製之「HFB2006M」、四國化成工業(股)製之「P-d」、「F-a」。 As a commercial item of the benzoxazine-based curing agent, "HFB2006M" manufactured by Showa Polymer Co., Ltd., "P-d" manufactured by Shikoku Chemical Industries Co., Ltd., and "F-a" are exemplified.

作為氰酸酯酯系硬化劑，雖並未特別限定，但例如可列舉酚醛清漆型(酚酚醛清漆型、烷基酚酚醛清漆型等)氰酸酯酯系硬化劑、雙環戊二烯型氰酸酯酯系硬化劑、雙酚型(雙酚A型、雙酚F型、雙酚S型等)氰酸酯酯系硬化劑、及此等一部分經三嗪化之預聚物等。作 為具體例，可列舉雙酚A二氰酸酯、聚酚氰酸酯(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)醚等之2官能氰酸酯樹脂、從酚酚醛清漆及甲酚酚醛清漆等所衍生之多官能氰酸酯樹脂、此等氰酸酯樹脂一部分經三嗪化之預聚物等。作為氰酸酯酯系硬化劑之市售品，例如可列舉Lonza Japan(股)製之「PT30」及「PT60」(皆為酚酚醛清漆型多官能氰酸酯酯樹脂)、「BA230」(雙酚A二氰酸酯的一部分或全部成為經三嗪化之三聚物的預聚物)等。 The cyanate ester-based curing agent is not particularly limited, and examples thereof include a novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type curing agent and dicyclopentadiene type cyanide. An ester ester-based curing agent, a bisphenol-type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate ester-based curing agent, and a part of the triazine-based prepolymer. Make Specific examples include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene)), 4,4'-methylene double (2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanide Acid ester) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-double (4 2-functional cyanic acid such as cyanate ester phenyl-1-(methylethylidene) benzene, bis(4-cyanate phenyl) sulfide, and bis(4-cyanate phenyl) ether An ester resin, a polyfunctional cyanate resin derived from a phenol novolak, a cresol novolak, or the like, and a pre-polymerized triazine-based prepolymer of such a cyanate resin. Examples of the commercially available product of the cyanate ester-based curing agent include "PT30" and "PT60" manufactured by Lonza Japan Co., Ltd. (all of which are phenol novolac type polyfunctional cyanate ester resins), and "BA230" ( A part or all of the bisphenol A dicyanate becomes a prepolymer of a triazineated terpolymer).

將(B)硬化劑之不揮發成分定為100質量%時，液狀酚系硬化劑的含量較佳為50質量%以上，更佳為60質量%以上，再更佳為70質量%以上、80質量%以上、或90質量%以上。該液狀酚系硬化劑的含量之上限並未特別限定，可為100質量%。 When the non-volatile content of the (B) curing agent is 100% by mass, the content of the liquid phenol-based curing agent is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more. 80% by mass or more, or 90% by mass or more. The upper limit of the content of the liquid phenol-based curing agent is not particularly limited, and may be 100% by mass.

(A)環氧樹脂與(B)硬化劑的量比，從使所得之絕緣層之機械強度或耐水性提昇的觀點來看，較佳為[環氧樹脂之環氧基之合計數]：[硬化劑之反應基之合計數]的比率為1：0.2~1：2的範圍，更佳為1：0.3~1：1.5之範圍，再更佳1：0.4~1：1的範圍。於此，所謂硬化劑之反應基，係活性羥基、活性酯基等，因硬化劑之種 類而不同。又，所謂環氧樹脂之環氧基的合計數，係針對全部之環氧樹脂將環氧當量除以各環氧樹脂之固形分質量的值進行合計之值，所謂硬化劑之反應基的合計數，係針對全部之硬化劑將反應基當量除以各硬化劑之固形分質量的值進行合計之值。 The ratio of the amount of the epoxy resin to the hardener (B) is preferably [the total number of epoxy groups of the epoxy resin] from the viewpoint of improving the mechanical strength or water resistance of the obtained insulating layer: The ratio of [the total number of reactive groups of the hardener] is in the range of 1:0.2 to 1:2, more preferably in the range of 1:0.3 to 1:1.5, still more preferably in the range of 1:0.4 to 1:1. Here, the reactive group of the curing agent is a reactive hydroxyl group, an active ester group, etc., due to the kind of hardener. Different from class to class. In addition, the total number of epoxy groups of the epoxy resin is a total value obtained by dividing the epoxy equivalent of each epoxy resin by the solid content of each epoxy resin, and the total of the reactive groups of the curing agent The number is a total value obtained by dividing the equivalent of the reaction group by the value of the solid content of each hardener for all the hardeners.

<(C)無機填充材> <(C) Inorganic filler>

在本發明之樹脂組成物，無機填充材，其特徵為包含(C1)平均粒徑0.1μm以上未滿3μm之無機填充材、(C2)平均粒徑3μm以上未滿10μm之無機填充材及(C3)平均粒徑10μm以上且35μm以下之無機填充材。藉此，可實現熱擴散性及對於金屬層之密著強度雙方皆優異的絕緣層。 In the resin composition of the present invention, the inorganic filler is characterized in that (C1) an inorganic filler having an average particle diameter of 0.1 μm or more and less than 3 μm, and (C2) an inorganic filler having an average particle diameter of 3 μm or more and less than 10 μm and ( C3) An inorganic filler having an average particle diameter of 10 μm or more and 35 μm or less. Thereby, an insulating layer excellent in both thermal diffusibility and adhesion strength to the metal layer can be achieved.

從實現熱擴散性及對於金屬層之密著強度雙方皆優異的絕緣層的觀點來看，較佳為將(C1)成分之平均粒徑定為dc1(μm)，將(C2)成分之平均粒徑定為dc2(μm)時，dc1及dc2滿足dc2-dc1≧0.5的關係，更佳為滿足dc2-dc1≧1.0的關係，再更佳為滿足dc2-dc1≧1.5、dc2-dc1≧2.0、dc2-dc1≧2.5、或dc2-dc1≧3.0的關係。差異dc2-dc1的上限較佳為9.0以下，更佳為8.0以下，再更佳為7.0以下、6.0以下、或5.0以下。 From the viewpoint of achieving thermal diffusivity and an insulating layer excellent in both of the adhesion strengths of the metal layers, it is preferable to set the average particle diameter of the (C1) component to d c1 (μm) and the component (C2). When the average particle diameter is set to d c2 (μm), d c1 and d c2 satisfy the relationship of d c2 -d c1 ≧0.5, more preferably satisfy the relationship of d c2 -d c1 ≧1.0, and more preferably satisfy d c2 - d c1 ≧ 1.5, d c2 - d c1 ≧ 2.0, d c2 - d c1 ≧ 2.5, or d c2 - d c1 ≧ 3.0. The upper limit of the difference d c2 - d c1 is preferably 9.0 or less, more preferably 8.0 or less, still more preferably 7.0 or less, 6.0 or less, or 5.0 or less.

實現熱擴散性及對於金屬層之密著強度雙方皆優異的絕緣層觀點來看，較佳為將(C3)成分之平均粒徑定為dc3(μm)時，dc2及dc3滿足dc3-dc2≧5.0的關 係，更佳為滿足dc3-dc2≧7.0的關係，再更佳為滿足dc3-dc2≧9.0、dc3-dc2≧10.0、dc3-dc2≧12.0、dc3-dc2≧14.0、或dc3-dc2≧15.0的關係。差異dc3-dc2之上限較佳為30.0以下，更佳為28.0以下，再更佳為26.0以下、24.0以下、22.0以下、或20.0以下。 From the viewpoint of achieving thermal diffusivity and an insulating layer excellent in both of the adhesion strengths of the metal layers, it is preferable that d c2 and d c3 satisfy d when the average particle diameter of the (C3) component is d c3 (μm). The relationship of c3 -d c2 ≧5.0 is more preferably to satisfy the relationship of d c3 -d c2 ≧7.0, and more preferably to satisfy d c3 -d c2 ≧9.0, d c3 -d c2 ≧10.0, d c3 -d c2 ≧ 12.0, d c3 - d c2 ≧ 14.0, or d c3 - d c2 ≧ 15.0. The upper limit of the difference d c3 -d c2 is preferably 30.0 or less, more preferably 28.0 or less, still more preferably 26.0 or less, 24.0 or less, 22.0 or less, or 20.0 or less.

在一實施形態，dc1、dc2及dc3係滿足dc2-dc1≧0.5及dc3-dc2≧5.0的關係。 In one embodiment, d c1 , d c2 and d c3 satisfy the relationship of d c2 -d c1 ≧0.5 and d c3 -d c2 ≧5.0.

無機填充材之平均粒徑可根據米氏(Mie)散射理論藉由雷射繞射．散射法來測定。具體而言藉由雷射繞射散射式粒度分布測定裝置，將無機填充材之粒度分布以體積基準作成，可藉由：其中位徑作為平均粒徑來測定。測定樣品較佳可使用將無機填充材藉由超音波使其分散於水中者。作為雷射繞射散射式粒度分布測定裝置，可使用(股)堀場製作所製「LA-500」、「LA-950」等。 The average particle size of the inorganic filler can be diffraction by laser according to the Mie scattering theory. Determine by scattering method. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and can be measured by using the position diameter as the average particle diameter. It is preferable to use a sample in which the inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" and "LA-950" manufactured by Horiba, Ltd. can be used.

(C1)成分藉由埋入(C2)成分、(C3)成分的間隙，有助於樹脂組成物(也就是絕緣層)之熱擴散性的提昇。(C1)成分又，在與(C2)成分及(C3)成分的組合，(C)成分全體的含量高的情況下，表現抑制熔融黏度上昇的效果。將(C)成分的含量定為100質量%的情況下，(C1)成分的含量即使於(C)成分的含量高的情況下，從可抑制熔融黏度的過度上昇的觀點、得到熱擴散性優異之絕緣層的觀點來看，較佳為5質量%以上，更佳為6質量%以上，再更佳為8質量%以上、10質量%以上、12質量%以上、14質量%以上、或15質量%以 上。該(C1)成分的含量之上限，從藉由半導體元件所產生的熱擴散於印刷配線板時，減少在界面(無機填充材-無機填充材間或無機填充材-金屬層間)之擴散電阻的觀點來看，較佳為40質量%以下，更佳為35質量%以下，再更佳為30質量%以下。 The (C1) component contributes to the improvement of the thermal diffusibility of the resin composition (that is, the insulating layer) by embedding the gap between the (C2) component and the (C3) component. In addition, when the content of the component (C) is high in combination with the component (C2) and the component (C3), the component (C1) exhibits an effect of suppressing an increase in melt viscosity. When the content of the component (C) is 100% by mass, the content of the component (C1) is such that the content of the component (C) is high, and the thermal diffusibility is obtained from the viewpoint of suppressing an excessive increase in the melt viscosity. From the viewpoint of the excellent insulating layer, it is preferably 5% by mass or more, more preferably 6% by mass or more, still more preferably 8% by mass or more, 10% by mass or more, 12% by mass or more, or 14% by mass or more, or 15% by mass on. When the upper limit of the content of the (C1) component is diffused from the heat generated by the semiconductor element to the printed wiring board, the diffusion resistance at the interface (between the inorganic filler-inorganic filler or the inorganic filler-metal layer) is reduced. From the viewpoint, it is preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less.

(C2)成分藉由埋入(C3)成分之間隙，有助於樹脂組成物(也就是絕緣層)之熱擴散性的提昇。(C2)成分又，較(C1)成分平均粒徑更大，亦有助於在熱擴散時之界面的擴散電阻的降低。將(C)成分的含量定為100質量%的情況下，(C2)成分的含量從得到熱擴散性優異之絕緣層的觀點來看，較佳為5質量%以上，更佳為6質量%以上，再更佳為8質量%以上、10質量%以上、12質量%以上、14質量%以上、或15質量%以上。該(C2)成分的含量之上限，從抑制熔融黏度的過度上昇的觀點來看，較佳為40質量%以下，更佳為35質量%以下，再更佳為30質量%以下。 The (C2) component contributes to the improvement of the thermal diffusibility of the resin composition (that is, the insulating layer) by embedding the gap of the (C3) component. The (C2) component, in turn, has a larger average particle diameter than the (C1) component, and also contributes to a decrease in the diffusion resistance at the interface at the time of thermal diffusion. When the content of the component (C) is 100% by mass, the content of the component (C2) is preferably 5% by mass or more, and more preferably 6% by mass, from the viewpoint of obtaining an insulating layer excellent in thermal diffusibility. More preferably, it is 8 mass % or more, 10 mass % or more, 12 mass % or more, 14 mass % or more, or 15 mass % or more. The upper limit of the content of the component (C2) is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less from the viewpoint of suppressing an excessive increase in the melt viscosity.

(C3)成分較(C1)成分、(C2)成分平均粒徑更大，使在熱擴散時之界面的擴散電阻的降低，非常有助於樹脂組成物(也就是絕緣層)之熱擴散性的提昇。將(C)成分的含量定為100質量%的情況下，(C3)成分的含量從得到熱擴散性優異之絕緣層的觀點來看，較佳為20質量%以上，更佳為30質量%以上，再更佳為40質量%以上、45質量%以上、50質量%以上、55質量%以上、或60質量%以上。該(C3)成分的含量之上限，從 良好保持(C)成分的填充狀態得到層合性及熱擴散性優異之樹脂組成物的觀點來看，較佳為90質量%以下，更佳為85質量%以下，再更佳為80質量%以下、75質量%以下、或70質量%以下。 The (C3) component has a larger average particle diameter than the (C1) component and the (C2) component, and the diffusion resistance of the interface at the time of thermal diffusion is lowered, which contributes to the thermal diffusivity of the resin composition (that is, the insulating layer). Improvement. When the content of the component (C) is 100% by mass, the content of the component (C3) is preferably 20% by mass or more, and more preferably 30% by mass from the viewpoint of obtaining an insulating layer excellent in thermal diffusibility. More preferably, it is 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more. The upper limit of the content of the (C3) component, From the viewpoint of obtaining a resin composition excellent in lamination property and thermal diffusibility, the filling state of the component (C) is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass. Hereinafter, it is 75 mass% or less, or 70 mass% or less.

據此，在適合之一實施形態，將(C)成分的含量定為100質量%的情況下，(C1)成分的含量為5質量%~40質量%，(C2)成分的含量為5質量%~40質量%，(C3)成分的含量為20質量%~90質量%。 According to this, in a case where the content of the component (C) is 100% by mass, the content of the component (C1) is 5% by mass to 40% by mass, and the content of the component (C2) is 5 mass. The content of the component (C3) is from 20% by mass to 90% by mass.

(C)成分中之(C1)、(C2)及(C3)成分的含量雖如上述，但從得到熱擴散性及對於金屬層之密著強度雙方更為優異之絕緣層的觀點來看，以(C3)成分的含量最高較佳。 The content of the components (C1), (C2), and (C3) in the component (C) is as described above, but from the viewpoint of obtaining an insulating layer which is more excellent in thermal diffusibility and adhesion strength to the metal layer, The content of the component (C3) is preferably the highest.

作為無機填充材，例如可列舉二氧化矽、氧化鋁、玻璃、堇青石、矽氧化物、硫酸鋇、滑石、黏土、雲母粉、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、氮化矽、碳化矽、氮化鋁、氮化錳、硼酸鋁、鈦酸鋇、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、鋯酸鋇、鋯酸鈣、磷酸鋯、及磷酸鎢酸鋯等。 Examples of the inorganic filler include cerium oxide, aluminum oxide, glass, cordierite, cerium oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, and magnesium oxide. Boron nitride, tantalum nitride, tantalum carbide, aluminum nitride, manganese nitride, aluminum borate, barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, Calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, and the like.

從得到熱擴散性優異之絕緣層的觀點來看，無機填充材適合包含較佳係熱傳導率為25W/m．K以上，更佳為50W/m．K以上，再更佳為75W/m．K以上，又再更佳為100W/m．K以上，特佳為125W/m．K以上、150W/m．K以上、175W/m．K以上、200W/m．K以上、或225W/m．K以上的無機填充材。該熱傳導率之上限雖並未特別限 定，但通常為400W/m．K以下。無機填充材之熱傳導率，例如可藉由熱流計法及溫度波分析法等之周知方法測定。 From the viewpoint of obtaining an insulating layer excellent in thermal diffusivity, the inorganic filler is preferably contained in a preferred thermal conductivity of 25 W/m. K or more, more preferably 50W/m. Above K, more preferably 75W/m. Above K, it is more preferably 100W/m. Above K, especially good is 125W/m. K or more, 150W/m. K or more, 175W/m. K or more, 200W/m. K or more, or 225W/m. An inorganic filler of K or more. The upper limit of the thermal conductivity is not particularly limited. Fixed, but usually 400W/m. Below K. The thermal conductivity of the inorganic filler can be measured, for example, by a known method such as a heat flow meter method or a temperature wave analysis method.

在一實施形態，無機填充材適合包含選擇自由氮化鋁、氧化鋁、氮化硼、氮化矽及碳化矽所構成之群組中之熱傳導率高的無機填充材，其中，適合包含氮化鋁、或氧化鋁。作為氮化鋁之市售品，例如可列舉(股)德山製「Shapal H」，作為氮化矽之市售品，例如可列舉電氣化學工業(股)製「SN-9S」。作為氧化鋁之市售品，例如可列舉日本輕金屬(股)製「AHP300」、昭和電工(股)製「ALUNABEADS1(註冊商標)CB」(例如、「CB-P05」、「CB-A30S」)。 In one embodiment, the inorganic filler is preferably an inorganic filler having a high thermal conductivity selected from the group consisting of aluminum nitride, aluminum oxide, boron nitride, tantalum nitride, and niobium carbide. Aluminum, or alumina. As a commercially available product of aluminum nitride, for example, "Shapal H" manufactured by Tokuyama Co., Ltd. can be cited. As a commercially available product of tantalum nitride, for example, "SN-9S" manufactured by Electrochemical Industry Co., Ltd. can be cited. For example, "AHP300" manufactured by Japan Light Metal Co., Ltd. and "ALUNABEADS1 (registered trademark) CB" (for example, "CB-P05" and "CB-A30S") manufactured by Showa Denko Co., Ltd. .

(C1)成分、(C2)成分及(C3)成分可由同一材料形成，亦可彼此由不同材料形成。又，(C1)成分、(C2)成分及(C3)成分之每一種可由1種材料形成，亦可由2種以上的材料的組合形成。其中，較佳為(C3)成分包含熱傳導率高的無機填充材，更佳為(C3)成分及(C2)成分包含熱傳導率高的無機填充材，再更佳為(C3)成分、(C2)成分及(C1)成分的全部包含熱傳導率高的無機填充材。 The (C1) component, the (C2) component, and the (C3) component may be formed of the same material or may be formed of different materials from each other. Further, each of the (C1) component, the (C2) component, and the (C3) component may be formed of one material or a combination of two or more materials. In particular, it is preferable that the component (C3) contains an inorganic filler having a high thermal conductivity, and it is more preferable that the component (C3) and the component (C2) contain an inorganic filler having a high thermal conductivity, and more preferably a component (C3) or (C2). The components and (C1) components all contain an inorganic filler having a high thermal conductivity.

無機填充材從提高耐濕性及分散性的觀點來看，可用胺基矽烷系偶合劑、環氧矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、有機矽氮烷化合物、鈦酸酯系偶合劑等之1種以上的表面處理劑進行處理。作為表面處理劑之市售品，例如可列舉信越化學工業(股)製 「KBM403」(3-環氧丙氧基丙基三甲氧基矽烷)、信越化學工業(股)製「KBM803」(3-巰基丙基三甲氧基矽烷)、信越化學工業(股)製「KBE903」(3-胺基丙基三乙氧基矽烷)、信越化學工業(股)製「KBM573」(N-苯基-3-胺基丙基三甲氧基矽烷)、信越化學工業(股)製「SZ-31」(六甲基二矽氮烷)等。 The inorganic filler may be an amine decane coupling agent, an epoxy decane coupling agent, a mercapto decane coupling agent, a decane coupling agent, an organic decazane compound, or a titanic acid from the viewpoint of improving moisture resistance and dispersibility. One or more surface treatment agents such as an ester coupling agent are treated. As a commercial product of a surface treatment agent, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxydecane), "KBM803" (3-mercaptopropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBE903" manufactured by Shin-Etsu Chemical Co., Ltd. "(3-Aminopropyltriethoxydecane), "KBM573" (N-phenyl-3-aminopropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldiazane) and the like.

藉由表面處理劑之表面處理的程度，可藉由每一無機填充材之單位表面積的碳量進行評估。每一無機填充材之單位表面積的碳量，從無機填充材之分散性提昇的觀點來看，較佳為0.02mg/m2以上，更佳為0.1mg/m2以上，再更佳為0.2mg/m2以上。另一方面，從防止樹脂清漆之熔融黏度或於薄片形態之熔融黏度的上昇的觀點來看，較佳為1mg/m2以下，更佳為0.8mg/m2以下，再更佳為0.5mg/m2以下。 The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of each inorganic filler. The amount of carbon per unit surface area of each inorganic filler is preferably 0.02 mg/m 2 or more, more preferably 0.1 mg/m 2 or more, and still more preferably 0.2 from the viewpoint of improving the dispersibility of the inorganic filler. mg / m 2 or more. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish or the increase in the melt viscosity of the sheet form, it is preferably 1 mg/m 2 or less, more preferably 0.8 mg/m 2 or less, still more preferably 0.5 mg. /m 2 or less.

每一無機填充材之單位表面積的碳量，可將表面處理後之無機填充材藉由溶劑(例如甲基乙基酮(MEK))洗淨處理後來測定。具體而言，作為溶劑，將充分量之MEK加入以表面處理劑進行表面處理之無機填充材，再於25℃進行5分鐘超音波洗淨。去除上清液，使固形分乾燥後，可使用碳分析計測定每一無機填充材之單位表面積的碳量。作為碳分析計，可使用(股)堀場製作所製「EMIA-320V」等。 The amount of carbon per unit surface area of each inorganic filler can be determined by washing the surface-treated inorganic filler with a solvent such as methyl ethyl ketone (MEK). Specifically, as a solvent, a sufficient amount of MEK was added to an inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning was performed at 25 ° C for 5 minutes. After the supernatant is removed and the solid fraction is dried, the amount of carbon per unit surface area of each inorganic filler can be determined using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

從得到熱擴散性優異之絕緣層的觀點來看，樹脂組成物中之無機填充材的含量，將樹脂組成物中之不 揮發成分定為100體積%的情況下，較佳為60體積%以上，更佳為65體積%以上。於包含組合特定之(A)~(C)成分之本發明的樹脂組成物，不僅不會使對於金屬層之密著強度降低，並且可進一步提高無機填充材的含量。例如，樹脂組成物中之無機填充材的含量可提高至66體積%以上、68體積%以上、70體積%以上、72體積%以上、74體積%以上或75體積%以上為止。 From the viewpoint of obtaining an insulating layer excellent in thermal diffusibility, the content of the inorganic filler in the resin composition is not in the resin composition. When the volatile component is 100% by volume, it is preferably 60% by volume or more, and more preferably 65% by volume or more. In the resin composition of the present invention containing the specific components (A) to (C), the adhesion strength to the metal layer is not lowered, and the content of the inorganic filler can be further increased. For example, the content of the inorganic filler in the resin composition can be increased to 66% by volume or more, 68% by volume or more, 70% by volume or more, 72% by volume or more, 74% by volume or more, or 75% by volume or more.

樹脂組成物中之無機填充材的含量之上限，從所得之絕緣層之機械強度的觀點來看，較佳為90體積%以下，更佳為85體積%以下。 The upper limit of the content of the inorganic filler in the resin composition is preferably 90% by volume or less, and more preferably 85% by volume or less from the viewpoint of mechanical strength of the obtained insulating layer.

<(D)硬化促進劑> <(D) hardening accelerator>

本發明之樹脂組成物可進一步包含硬化促進劑。藉由使用硬化促進劑，可提高對於金屬層之密著強度。 The resin composition of the present invention may further comprise a hardening accelerator. By using a hardening accelerator, the adhesion strength to the metal layer can be improved.

作為硬化促進劑，例如可列舉磷系硬化促進劑、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，磷系硬化促進劑、胺系硬化促進劑，較佳為咪唑系硬化促進劑，再更佳磷系硬化促進劑。硬化促進劑可1種單獨使用，亦可組合2種以上使用。 Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, an lanthanum-based curing accelerator, and a metal-based curing accelerator, and a phosphorus-based curing accelerator and an amine-based curing accelerator. It is preferably an imidazole-based hardening accelerator, and more preferably a phosphorus-based hardening accelerator. The curing accelerator may be used alone or in combination of two or more.

作為磷系硬化促進劑，例如可列舉四取代鏻鹽、膦(例如三苯基膦、三對甲苯基膦、二苯基環己基膦、三環己基膦、1,4-雙二苯基膦基丁烷等)，較佳為三苯基膦、四取代鏻鹽，更佳為四取代鏻鹽。 Examples of the phosphorus-based hardening accelerator include tetra-substituted phosphonium salts and phosphines (for example, triphenylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine, and 1,4-bisdiphenylphosphine). Butylbutane or the like) is preferably a triphenylphosphine or a tetrasubstituted phosphonium salt, more preferably a tetrasubstituted phosphonium salt.

四取代鏻鹽較佳由選自四烷基鏻陽離子(例如四丁基鏻、三丁基己基鏻、丁基三苯基鏻等)、四芳基鏻陽離子(例如四苯基鏻等)中之1種以上的陽離子所形成。 The tetra-substituted sulfonium salt is preferably selected from the group consisting of a tetraalkylphosphonium cation (for example, tetrabutylphosphonium, tributylhexylphosphonium, butyltriphenylphosphonium, etc.), a tetraarylphosphonium cation (for example, tetraphenylphosphonium, etc.). One or more kinds of cations are formed.

四取代鏻鹽較佳為由選自四取代硼酸鹽陰離子(例如四苯基硼酸鹽陰離子)、硫氰酸酯陰離子、二氰胺陰離子、4,4’-二羥基二苯基碸陰離子、胺基酸離子(例如天冬胺酸離子、麩胺酸離子、甘胺酸離子、丙胺酸離子、苯基丙胺酸離子)、N-醯基胺基酸離子(例如N-苯甲醯基丙胺酸離子、N-乙醯基苯基丙胺酸離子、N-乙醯基甘胺酸離子)、羧酸陰離子(例如甲酸離子、乙酸離子、癸酸離子、2-吡咯烷酮-5-羧酸離子、α-硫辛酸離子、乳酸離子、酒石酸離子、馬尿酸離子、N-甲基馬尿酸離子、苯甲酸離子)、鹵素離子中之1種以上的陽離子所形成。再更佳選自4,4’-二羥基二苯基碸陰離子、胺基酸離子、及羧酸陰離子中之1種以上。 The tetrasubstituted phosphonium salt is preferably selected from the group consisting of a tetrasubstituted borate anion (for example, tetraphenyl borate anion), a thiocyanate anion, a dicyanamide anion, a 4,4'-dihydroxydiphenyl anthracene anion, an amine. Acid ion (eg aspartic acid ion, glutamic acid ion, glycine ion, alanine ion, phenylalanine ion), N-decylamino acid ion (eg N-benzamide amino alanine) Ionic, N-ethylcyanophenylalanine ion, N-ethinylglycine ion), carboxylate anion (eg formate ion, acetate ion, citric acid ion, 2-pyrrolidone-5-carboxylic acid ion, α - a lipoic acid ion, a lactate ion, a tartaric acid ion, a hippuric acid ion, an N-methyl hippuric acid ion, a benzoic acid ion, or one or more cations of a halogen ion. Further, it is more preferably one or more selected from the group consisting of a 4,4'-dihydroxydiphenylphosphonium anion, an amino acid ion, and a carboxylic acid anion.

作為胺系硬化促進劑，例如可列舉三乙基胺、三丁基胺等之三烷基胺、4-二甲基胺基吡啶、苄基二甲基胺、2,4,6,-參(二甲基胺基甲基)酚、1,8-二氮雜雙環(5,4,0)-十一碳烯等，以4-二甲基胺基吡啶、1,8-二氮雜雙環(5,4,0)-十一碳烯較佳。 Examples of the amine-based curing accelerator include a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, and a ginseng. (Dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., with 4-dimethylaminopyridine, 1,8-diaza Bicyclic (5,4,0)-undecene is preferred.

作為咪唑系硬化促進劑，例如可列舉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-2-十一烷基咪唑鎓偏苯三酸酯、1-氰乙基-2-苯基咪唑鎓偏苯三酸酯、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-羥基甲基咪唑、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-苯基咪唑啉等之咪唑化合物及咪唑化合物與環氧樹脂的加成物(Adduct)，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 group. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methyl Imidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl Base-2-undecyl imidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-three Oxazine, 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-ten An imidazole compound such as dialkyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline or 2-phenylimidazoline, and an adduct of an imidazole compound and an epoxy resin (Adduct), Preferred is 2-ethyl-4-methylimidazole, 1-benzyl-2 - phenylimidazole.

作為咪唑系硬化促進劑，可使用市售品，例如可列舉三菱化學(股)製之「P200-H50」等。 A commercially available product can be used as the imidazole-based hardening accelerator, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

作為胍系硬化促進劑，例如可列舉雙氰胺、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、1,5,7-三氮雜雙環[4.4.0]癸-5-烯、7-甲基-1,5,7-三氮雜雙環[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，較佳為雙氰胺、1,5,7-三氮雜雙環[4.4.0]癸-5-烯。 Examples of the oxime-based hardening accelerator include dicyandiamide, 1-methyl hydrazine, 1-ethyl hydrazine, 1-cyclohexyl hydrazine, 1-phenyl fluorene, 1-(o-methylphenyl) fluorene, and dimethyl Base, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0]non-5-ene, 7-methyl-1 , 5,7-triazabicyclo[4.4.0]non-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-Dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenyl Biguanide, 1-(o-methylphenyl)biguanide, etc., preferably dicyandiamide, 1,5,7-triazabicyclo[4.4.0]non-5-ene.

作為金屬系硬化促進劑，例如可列舉鈷、銅、鋅、鐵、鎳、錳、錫等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之具體例，可列舉鈷(II)乙醯丙酮酸鹽(Acetylacetonate)、鈷(III)乙醯丙酮酸鹽等之有機鈷錯合物、銅(II)乙醯丙酮酸鹽等之有機銅錯合物、鋅(II)乙醯丙酮酸鹽等之有機鋅錯合物、鐵(III)乙醯丙酮酸鹽等之有機鐵錯合物、鎳(II)乙醯丙酮酸鹽等之有機鎳錯合物、錳(II)乙醯丙酮酸鹽等之有機錳錯合物等。作為有機金屬鹽，例如可列舉辛酸鋅、辛酸錫、環烷酸鋅、環烷酸鈷、硬脂酸錫、硬脂酸鋅等。 Examples of the metal-based curing accelerator 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) acetyl acetonate (Acetylacetonate) and cobalt (III) acetoacetate, and copper (II) acetoacetate. An organic copper complex such as a salt, an organic zinc complex such as zinc (II) acetoacetate, an organic iron complex such as iron (III) acetoacetate, or nickel (II) acetonitrile An organic nickel complex such as an acid salt or an organic manganese complex such as manganese (II) acetoacetate or the like. Examples of the organic metal salt include zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

樹脂組成物中之硬化促進劑的含量，較佳為將(A)環氧樹脂及(B)硬化劑之不揮發成分之合計定為100質量%時，以0.05質量%~3質量%的範圍使用。 The content of the hardening accelerator in the resin composition is preferably in the range of 0.05% by mass to 3% by mass when the total of the nonvolatile components of the (A) epoxy resin and the (B) curing agent is 100% by mass. use.

<(E)碳二醯亞胺化合物> <(E)carbodiimide compound>

本發明之樹脂組成物可進一步包含碳二醯亞胺化合物。本發明者們發現藉由與上述之(A)~(C)成分組合來使用碳二醯亞胺化合物，可實現對於金屬層呈現更為良好之密著強度的樹脂組成物(也就是絕緣層)。 The resin composition of the present invention may further comprise a carbodiimide compound. The present inventors have found that by using a carbodiimide compound in combination with the above components (A) to (C), a resin composition which exhibits a better adhesion strength to a metal layer (that is, an insulating layer) can be realized. ).

碳二醯亞胺化合物係於1分子中具有1個以上碳二醯亞胺基(-N=C=N-)之化合物。從提高對於金屬層之密著強度的觀點來看，作為碳二醯亞胺化合物，較佳 為於1分子中具有2個以上碳二醯亞胺基之化合物。碳二醯亞胺化合物可1種單獨使用，亦可組合2種以上使用。 The carbodiimide compound is a compound having one or more carbodiimide groups (-N=C=N-) in one molecule. From the viewpoint of improving the adhesion strength to the metal layer, as the carbodiimide compound, it is preferred It is a compound having two or more carbon diimine groups in one molecule. The carbodiimide compound may be used alone or in combination of two or more.

在一實施形態，本發明之樹脂組成物所包含之碳二醯亞胺化合物係含有下述式(2)表示之結構單位。 In one embodiment, the carbodiimide compound contained in the resin composition of the present invention contains a structural unit represented by the following formula (2).

(式中，X係表示伸烷基、環伸烷基或伸芳基，此等可具有取代基；p係表示1~5之整數；X複數存在時，該等可為相同或相異；*係表示鍵結手)。 (wherein X represents an alkylene group, a cycloalkylene group or an extended aryl group, and these may have a substituent; p represents an integer of 1 to 5; and when X is present, these may be the same or different; * is the key to the hand).

X表示之伸烷基之碳原子數較佳為1~20，更佳為1~10，再更佳為1~6、1~4、或1~3。X表示之環伸烷基之碳原子數較佳為3~20，更佳為3~12，再更佳為3~6。X表示之伸芳基係從芳香族烴去除2個芳香環上之氫原子之基。該伸芳基之碳原子數較佳為6~24，更佳為6~18，再更佳為6~14，又再更佳為6~10。於該碳原子數未包含取代基之碳原子數。 The number of carbon atoms of the alkyl group represented by X is preferably from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 6, from 1 to 4, or from 1 to 3. The number of carbon atoms of the cycloalkyl group represented by X is preferably from 3 to 20, more preferably from 3 to 12, still more preferably from 3 to 6. The extended aryl group represented by X removes a hydrogen atom from two aromatic rings from an aromatic hydrocarbon. The number of carbon atoms of the aryl group is preferably from 6 to 24, more preferably from 6 to 18, still more preferably from 6 to 14, and even more preferably from 6 to 10. The number of carbon atoms in which the number of carbon atoms does not contain a substituent.

在與(A)~(C)成分的組合，從實現對於金屬層呈現更為良好之密著強度的樹脂組成物(也就是絕緣層)的觀點來看，較佳為X為伸烷基或環伸烷基，此等可具有取代基。 In combination with the components (A) to (C), from the viewpoint of realizing a resin composition (i.e., an insulating layer) which exhibits a better adhesion strength to the metal layer, X is preferably an alkyl group or A cycloalkyl group, which may have a substituent.

作為取代基雖並未特別限定，但例如可列舉鹵素原子、烷基、烷氧基、環烷基、環烷氧基、芳基、芳 氧基、醯基及醯氧基。作為取代基使用之烷基、烷氧基的碳原子數較佳為1~20，更佳為1~10，再更佳為1~6、1~4、或1~3。作為取代基使用之環烷基、環烷氧基的碳原子數較佳為3~20，更佳為3~12，再更佳為3~6。作為取代基使用之芳基的碳原子數較佳為6~24，更佳為6~18，再更佳為6~14，又再更佳為6~10。作為取代基使用之芳氧基的碳原子數較佳為6~24，更佳為6~18，再更佳為6~14，又再更佳為6~10。作為取代基使用之醯基，係指式：-C(=O)-R1表示之基(式中，R1係表示烷基或芳基)。R1表示之烷基的碳原子數較佳為1~20，更佳為1~10，再更佳為1~6、1~4、或1~3。R1表示之芳基的碳原子數較佳為6~24，更佳為6~18，再更佳為6~14，又再更佳為6~10。作為取代基使用之醯氧基，係指式：-O-C(=O)-R1表示之基(式中，R1係表示與上述相同意義)。其中，作為取代基，較佳為烷基、烷氧基、及醯氧基，更佳為烷基。 The substituent is not particularly limited, and examples thereof include a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, an aryloxy group, a decyl group, and a decyloxy group. The number of carbon atoms of the alkyl group or alkoxy group used as the substituent is preferably from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 6, from 1 to 4, or from 1 to 3. The number of carbon atoms of the cycloalkyl group or the cycloalkoxy group used as the substituent is preferably from 3 to 20, more preferably from 3 to 12, still more preferably from 3 to 6. The number of carbon atoms of the aryl group used as the substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and still more preferably 6 to 10. The number of carbon atoms of the aryloxy group used as the substituent is preferably 6 to 24, more preferably 6 to 18, still more preferably 6 to 14, and still more preferably 6 to 10. The thiol group used as a substituent means a group represented by the formula: -C(=O)-R 1 (wherein R 1 represents an alkyl group or an aryl group). The alkyl group represented by R 1 preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 6, 1 to 4 or 1 to 3 carbon atoms. The aryl group represented by R 1 preferably has 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms. The acyl group used as a substituent group, shall mean the formula: a group represented by the (formula, R 1 is the same meaning as the above-described system represents a) -OC (= O) -R. Among them, as the substituent, an alkyl group, an alkoxy group, and a decyloxy group are preferred, and an alkyl group is more preferred.

式(2)中，p較佳為1~4，更佳為2~4，再更佳為2或3。 In the formula (2), p is preferably from 1 to 4, more preferably from 2 to 4, still more preferably 2 or 3.

式(2)中，X為複數存在情況，該等可為相同，亦可為相異。在適合之一實施形態，至少一個X為伸烷基或環伸烷基，此等可具有取代基。 In the formula (2), X is a plural case, and the like may be the same or may be different. In a suitable embodiment, at least one X is an alkylene or cycloalkylene group, which may have a substituent.

在適合之一實施形態，將碳二醯亞胺化合物，碳二醯亞胺化合物之分子全體的質量定為100質量%時，在較佳為50質量%以上，更佳為60質量%以上，再 更佳為70質量%以上，又再更佳為80質量%以上或90質量%以上，含有式(2)表示之結構單位。碳二醯亞胺化合物去除末端結構，可實質上成為式(2)表示之結構單位。作為碳二醯亞胺化合物之末端結構，雖並未特別限定，但例如可列舉烷基、環烷基及芳基，此等可具有取代基。作為末端結構使用之烷基、環烷基、芳基，係與針對可具有X表示之基的取代基所說明之烷基、環烷基、芳基相同即可。又，可具有作為末端結構使用之基的取代基，與可具有X表示之基的取代基相同即可。 In a preferred embodiment, when the mass of the entire molecule of the carbodiimide compound or the carbodiimide compound is 100% by mass, it is preferably 50% by mass or more, and more preferably 60% by mass or more. again More preferably, it is 70% by mass or more, and more preferably 80% by mass or more or 90% by mass or more, and the structural unit represented by the formula (2) is contained. The carbodiimide compound removes the terminal structure and can substantially become a structural unit represented by the formula (2). The terminal structure of the carbodiimide compound is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group, and these may have a substituent. The alkyl group, the cycloalkyl group, and the aryl group used as the terminal structure may be the same as the alkyl group, the cycloalkyl group, and the aryl group described for the substituent which may have a group represented by X. Further, a substituent which may have a group used as a terminal structure may be the same as a substituent which may have a group represented by X.

碳二醯亞胺化合物可使用市售品。作為市售之碳二醯亞胺化合物，例如可列舉日清紡化學(股)製之Carbodilite(註冊商標)V-02B、V-03、V-04K、V-07及V-09、萊茵化學公司製之Stabaxol(註冊商標)P、P400、及Hykagil 510。 A commercially available product can be used as the carbodiimide compound. As a commercially available carbodiimide compound, for example, Carbodilite (registered trademark) V-02B, V-03, V-04K, V-07, and V-09 manufactured by Nisshinbo Chemical Co., Ltd., manufactured by Rhein Chemie Co., Ltd. Stabaxol (registered trademark) P, P400, and Hykagil 510.

樹脂組成物中之碳二醯亞胺化合物的含量較佳為0.1質量%以上，更佳為0.2質量%以上、0.3質量%以上、0.4質量%以上或0.5質量%以上。碳二醯亞胺化合物的含量之上限雖並未特別限定，但通常為可成為5質量%以下、3質量%以下、1質量%以下等。 The content of the carbodiimide compound in the resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more, or 0.5% by mass or more. The upper limit of the content of the carbodiimide compound is not particularly limited, but is usually 5% by mass or less, 3% by mass or less, and 1% by mass or less.

<(F)熱塑性樹脂> <(F) thermoplastic resin>

本發明之樹脂組成物可進一步包含熱塑性樹脂。藉由使用熱塑性樹脂，可得到具有充分之可撓性，且操作性優異之接著薄膜，同時可得到對於金屬層呈現良好之密著強 度的樹脂組成物層(也就是絕緣層)。 The resin composition of the present invention may further comprise a thermoplastic resin. By using a thermoplastic resin, a film having sufficient flexibility and excellent handleability can be obtained, and at the same time, a good adhesion to the metal layer can be obtained. The resin composition layer (that is, the insulating layer).

作為熱塑性樹脂，例如可列舉苯氧基樹脂、聚乙烯醇縮醛樹脂、聚烯烴樹脂、聚丁二烯樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚碸樹脂、聚醚碸樹脂、聚伸苯基醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂。熱塑性樹脂可1種單獨使用、或組合2種以上使用。 Examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polyolefin resin, a polybutadiene resin, a polyimide resin, a polyamide amide resin, and a polyether quinone resin. Polyanthracene resin, polyether oxime resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin. The thermoplastic resin may be used singly or in combination of two or more.

熱塑性樹脂之聚苯乙烯換算之重量平均分子量較佳為8,000~70,000的範圍，更佳為10,000~60,000的範圍，再更佳為20,000~60,000的範圍。熱塑性樹脂之聚苯乙烯換算之重量平均分子量係以凝膠滲透層析(GPC)法測定。具體而言，熱塑性樹脂之聚苯乙烯換算之重量平均分子量，使用(股)島津製作所製LC-9A/RID-6A作為測定裝置，使用昭和電工(股)製Shodex K-800P/K-804L/K-804L作為管柱，使用氯仿等作為移動相，將管柱溫度在40℃測定，可使用標準聚苯乙烯之檢量線算出。 The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, still more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene is used as a measuring device using LC-9A/RID-6A manufactured by Shimadzu Corporation, and Shodex K-800P/K-804L/ by Showa Denko Co., Ltd. K-804L is used as a column, and chloroform or the like is used as a mobile phase, and the column temperature is measured at 40 ° C, and can be calculated using a standard polystyrene calibration line.

作為苯氧基樹脂，例如可列舉具有選擇自由雙酚A骨架、雙酚F骨架、雙酚S骨架、雙酚苯乙酮骨架、酚醛清漆骨架、聯苯骨架、茀骨架、雙環戊二烯骨架、降莰烯骨架、萘骨架、蔥骨架、金剛烷骨架、萜烯骨架、及三甲基環已烷骨架所構成之群組中之1種以上骨架的苯氧基樹脂。苯氧基樹脂之末端可為酚性羥基、環氧基等之任一種官能基。苯氧基樹脂可1種單獨使用，亦可組 合2種以上使用。作為苯氧基樹脂之具體例，可列舉三菱化學(股)製之「1256」及「4250」(皆為含有雙酚A骨架之苯氧基樹脂)、「YX8100」(含有雙酚S骨架之苯氧基樹脂)、及「YX6954」(含有雙酚苯乙酮骨架之苯氧基樹脂，其他，亦可列舉新日鐵住金化學(股)製之「FX280」及「FX293」、三菱化學(股)製之「YL7553」、「YL6794」、「YL7213」、「YL7290」及「YL7482」等。 Examples of the phenoxy resin include a free bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolak skeleton, a biphenyl skeleton, an anthracene skeleton, and a dicyclopentadiene skeleton. A phenoxy resin having one or more kinds of skeletons in the group consisting of a norbornene skeleton, a naphthalene skeleton, an onion skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any one of a phenolic hydroxyl group and an epoxy group. Phenoxy resin can be used alone or in combination Use in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton) and "YX8100" (including a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation. "Phenoxy resin" and "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton, and others, "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., Mitsubishi Chemical (" "YL7553", "YL6794", "YL7213", "YL7290" and "YL7482", etc.

作為聚乙烯醇縮醛樹脂，例如可列舉聚乙烯醇縮甲醛樹脂、聚乙烯醇縮丁醛樹脂，較佳為聚乙烯醇縮丁醛樹脂。作為聚乙烯醇縮醛樹脂之具體例，例如可列舉電氣化學工業(股)製之「電化縮丁醛4000-2」、「電化縮丁醛5000-A」、「電化縮丁醛6000-C」、「電化縮丁醛6000-EP」、積水化學工業(股)製之S-LEC BH系列、BX系列、KS系列、BL系列、BM系列等。 Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "electrodinated butyral 4000-2", "electrodinated butyral 5000-A", and "electrodinated butyral 6000-C" manufactured by Electrochemical Industry Co., Ltd. "S-LEC BH series, BX series, KS series, BL series, BM series, etc.", "Electrified butyral 6000-EP", Sekisui Chemical Industry Co., Ltd.

作為聚醯亞胺樹脂之具體例，可列舉新日本理化(股)製之「RIKACOAT SN20」及「RIKACOAT PN20」。作為聚醯亞胺樹脂之具體例，又，可列舉使2官能性羥基末端聚丁二烯、二異氰酸酯化合物及四元酸酐進行反應所得之線狀聚醯亞胺(日本特開2006-37083號公報記載之聚醯亞胺)、含有聚矽氧烷骨架之聚醯亞胺(日本特開2002-12667號公報及日本特開2000-319386號公報等所記載之聚醯亞胺)等之改質聚醯亞胺。 Specific examples of the polyimine resin include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. Specific examples of the polyimine resin include a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (JP-A-2006-37083) The polyimine which is described in the above-mentioned publication, and the polyimine which contains a polyoxyalkylene skeleton (polyimine) described in JP-A-2002-12667 and JP-A-2000-319386, etc. Polyimine.

作為聚醯胺醯亞胺樹脂之具體例，可列舉東 洋紡績(股)製之「VYLOMAX HR11NN」及「VYLOMAX HR16NN」。作為聚醯胺醯亞胺樹脂之具體例，又，可列舉日立化成工業(股)製之「KS9100」、「KS9300」(含有聚矽氧烷骨架之聚醯胺醯亞胺)等之改質聚醯胺醯亞胺。 Specific examples of the polyamidoximine resin include the east "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Yangfang Performance Co., Ltd. Further, as a specific example of the polyamidoximine resin, a modification of "KS9100" and "KS9300" (polyamide containing a polyoxyalkylene skeleton) manufactured by Hitachi Chemical Co., Ltd. Polyamidoximine.

作為聚醚碸樹脂之具體例，可列舉住友化學(股)製之「PES5003P」等。 Specific examples of the polyether oxime resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

作為聚碸樹脂之具體例，可列舉Solvay Advanced Polymers(股)製之聚碸「P1700」、「P3500」等。 Specific examples of the polybenzazole resin include polydiprene "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

其中，在與(A)~(C)成分的組合，從得到對於金屬層之密著強度更良好之絕緣層的觀點來看，作為熱塑性樹脂，較佳為苯氧基樹脂、聚乙烯醇縮醛樹脂。據此在適合之一實施形態，熱塑性樹脂係包含選擇自由苯氧基樹脂及聚乙烯醇縮醛樹脂所構成之群組中之1種以上。 In the combination with the components (A) to (C), from the viewpoint of obtaining an insulating layer having a better adhesion strength to the metal layer, the thermoplastic resin is preferably a phenoxy resin or a polyvinyl alcohol. Aldehyde resin. According to one embodiment, the thermoplastic resin is one or more selected from the group consisting of a free phenoxy resin and a polyvinyl acetal resin.

樹脂組成物中之熱塑性樹脂的含量較佳為0.1質量%~20質量%，更佳為0.5質量%~10質量%。 The content of the thermoplastic resin in the resin composition is preferably from 0.1% by mass to 20% by mass, more preferably from 0.5% by mass to 10% by mass.

<(G)其他添加成分> <(G) Other added ingredients>

本發明之樹脂組成物如有必要，可進一步包含選擇自由阻燃劑及有機填充材所構成之群組中之1種以上的添加劑。 The resin composition of the present invention may further contain one or more additives selected from the group consisting of a free flame retardant and an organic filler, if necessary.

-阻燃劑- - Flame retardant -

作為阻燃劑，例如可列舉有機磷系阻燃劑、含有有機系氮之磷化合物、氮化合物、矽氧系阻燃劑、金屬氫氧化物等。阻燃劑可1種單獨使用、或組合2種以上使用。樹脂組成物中之阻燃劑的含量雖並未特別限定，但較佳為0.5質量%~10質量%，更佳為0.8質量%~9質量%。 Examples of the flame retardant include an organic phosphorus-based flame retardant, a phosphorus compound containing an organic nitrogen, a nitrogen compound, a rhodium-based flame retardant, and a metal hydroxide. The flame retardant may be used singly or in combination of two or more. The content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5% by mass to 10% by mass, and more preferably 0.8% by mass to 9% by mass.

-有機填充材- -Organic filler -

作為有機填充材，可使用形成印刷配線板之絕緣層時所使用之任意有機填充材，可列舉橡膠粒子、聚醯胺微粒子、矽氧粒子等，較佳為橡膠粒子。樹脂組成物中之有機填充材的含量較佳為1質量%~10質量%，更佳為2質量%~5質量%。 As the organic filler, any organic filler used in forming the insulating layer of the printed wiring board can be used, and examples thereof include rubber particles, polyamide fine particles, and xenon particles, and rubber particles are preferable. The content of the organic filler in the resin composition is preferably from 1% by mass to 10% by mass, more preferably from 2% by mass to 5% by mass.

-其他成分- -Other ingredients -

本發明之樹脂組成物如有必要可包含其他成分。作為該其他成分，例如可列舉有機銅化合物、有機鋅化合物及有機鈷化合物等之有機金屬化合物、以及分散劑、增黏劑、消泡劑、整平劑、及著色劑等之樹脂添加劑等。 The resin composition of the present invention may contain other components as necessary. Examples of the other component include an organic metal compound such as an organic copper compound, an organic zinc compound, and an organic cobalt compound, and a resin additive such as a dispersant, a thickener, an antifoaming agent, a leveling agent, and a coloring agent.

本發明之樹脂組成物之調製方法並非被特別限定者，例如可列舉將摻合成分視必要而添加溶劑等，使用回轉混合機等進行混合．分散之方法等。 The preparation method of the resin composition of the present invention is not particularly limited, and for example, a solvent or the like may be added as necessary in the blending synthesis, and the mixture may be mixed using a rotary mixer or the like. Dispersion method, etc.

本發明之樹脂組成物係提供熱擴散性及對於金屬層之密著強度雙方皆優異之硬化物(絕緣層)。據此 本發明之樹脂組成物可適合作為用以形成印刷配線板之絕緣層的樹脂組成物(印刷配線板之絕緣層用樹脂組成物)使用，可更適合作為用以形成印刷配線板之層間絕緣層的樹脂組成物(印刷配線板之層間絕緣層用樹脂組成物)使用。又，本發明之樹脂組成物由於呈現適度的熔融黏度，零件嵌入性優異，亦可適合使用於印刷配線板為零件內藏電路板的情況。亦即，本發明之樹脂組成物可適合作為用以嵌入零件內藏電路板之零件的樹脂組成物(零件嵌入用樹脂組成物)使用。本發明之樹脂組成物，又可使用在選擇自由接著薄膜及預浸料所構成之群組中之薄片狀層合材料、防焊(Solder resist)、底部填充材、芯片焊接(Die bonding)材、半導體密封材、埋孔樹脂、零件嵌入樹脂等視樹脂組成物為必要之用途的廣大範圍。 The resin composition of the present invention provides a cured product (insulating layer) excellent in both heat diffusibility and adhesion strength to a metal layer. According to this The resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (a resin composition for an insulating layer of a printed wiring board), and can be more suitably used as an interlayer insulating layer for forming a printed wiring board. The resin composition (resin composition for the interlayer insulating layer of the printed wiring board) is used. Further, the resin composition of the present invention exhibits an appropriate melt viscosity and is excellent in component embedding property, and can be suitably used in a case where a printed wiring board is a component-embedded circuit board. In other words, the resin composition of the present invention can be suitably used as a resin composition (resin composition for component embedding) for embedding a component of a component-embedded circuit board. In the resin composition of the present invention, a sheet-like laminate, a solder resist, an underfill material, and a die bonding material in a group selected from the group consisting of a film and a prepreg can be used. A wide range of applications such as semiconductor sealing materials, buried resin, and component-embedded resins are necessary for use.

本發明之樹脂組成物，由於提供熱擴散性及對於金屬層之密著強度雙方皆優異之硬化物，故在功率半導體裝置，可適合使用在半導體模組與金屬放熱體的接著。藉此，可更有效率將功率半導體元件所產生的熱擴散至金屬放熱體。 Since the resin composition of the present invention provides a cured product excellent in both thermal diffusibility and adhesion strength to a metal layer, it can be suitably used in a power semiconductor device in conjunction with a semiconductor module and a metal heat radiator. Thereby, the heat generated by the power semiconductor element can be more efficiently diffused to the metal heat radiator.

本發明之樹脂組成物進而可使用在要求高熱傳導性之各種用途。 The resin composition of the present invention can be used in various applications requiring high thermal conductivity.

[接著薄膜] [Next film]

本發明之樹脂組成物雖亦可以清漆狀態進行塗佈來使用，工業上一般適合以接著薄膜之形態使用。 The resin composition of the present invention can also be used in the form of a varnish, and is generally industrially suitable for use as a film.

在一實施形態，接著薄膜係包含支持體、與和該支持體接合之樹脂組成物層(接著層)而成，樹脂組成物層(接著層)由本發明之樹脂組成物所構成。 In one embodiment, the film is formed of a support and a resin composition layer (adjacent layer) bonded to the support, and the resin composition layer (adhesion layer) is composed of the resin composition of the present invention.

作為支持體，例如可列舉由塑膠材料所構成之薄膜、金屬箔、脫膜紙，較佳為由塑膠材料所構成之薄膜、金屬箔。 Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material or a metal foil is preferable.

使用由塑膠材料所構成之薄膜作為支持體時，作為塑膠材料，例如可列舉聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)等之聚酯、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)等之丙烯醯基、環狀聚烯烴、三乙醯基纖維素(TAC)、聚醚硫化物(PES)、聚醚酮、聚醯亞胺等。其中，較佳為聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯，特佳為便宜的聚對苯二甲酸乙二酯。 When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and polycarbonate. (PC), polymethyl methacrylate (PMMA), etc., propylene fluorenyl, cyclic polyolefin, triethyl fluorenyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimine Wait. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and polyethylene terephthalate is particularly preferred.

使用金屬箔作為支持體時，作為金屬箔，例如可列舉銅箔、鋁箔等，較佳為銅箔。作為銅箔，可使用由銅之單金屬所構成之箔，亦可使用由銅與其他金屬(例如錫、鉻、銀、鎂、鎳、鋯、矽、鈦等)的合金所構成之箔。 When a metal foil is used as the support, examples of the metal foil include a copper foil, an aluminum foil, and the like, and a copper foil is preferable. As the copper foil, a foil composed of a single metal of copper may be used, and a foil composed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, hafnium, titanium, or the like) may be used.

支持體可於與樹脂組成物層接合側的表面實施霧面處理(Mat processing)、電暈處理。又，作為支持體，可使用於與樹脂組成物層接合側的表面具有脫膜層之附脫膜層的支持體。作為附脫膜層的支持體之脫膜層所使用之脫膜劑，例如可列舉選擇自由醇酸(Alkyd)樹 脂、烯烴樹脂、胺基甲酸乙酯樹脂、及矽氧樹脂所構成之群組中之1種以上的脫膜劑。作為脫膜劑之市售品，例如可列舉醇酸樹脂系脫膜劑，即Lintec(股)製之「SK-1」、「AL-5」、「AL-7」等。 The support may be subjected to mat processing or corona treatment on the surface on the side joined to the resin composition layer. Further, as the support, a support for the release layer of the release layer may be provided on the surface on the side where the resin composition layer is joined. As the release agent used for the release layer of the support with the release layer, for example, a free alkyd tree can be cited. One or more kinds of release agents selected from the group consisting of a fat, an olefin resin, a urethane resin, and a silicone resin. The commercially available product of the release agent may, for example, be an alkyd resin-based release agent, that is, "SK-1", "AL-5", "AL-7" manufactured by Lintec Co., Ltd., or the like.

支持體的厚度雖並未特別限定，但較佳為5μm~75μm的範圍，更佳為10μm~60μm的範圍。尚，支持體為附脫膜層的支持體的情況下，較佳為附脫膜層的支持體全體的厚度為上述範圍。 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. When the support is a support having a release layer, the thickness of the entire support having the release layer is preferably in the above range.

樹脂組成物層之厚度雖亦視用途而定，但從在層間(導體層-絕緣層-導體層、半導體模組-硬化物-金屬放熱體等)，使熱有效率擴散的觀點來看，較佳為200μm以下，更佳為180μm以下，再更佳為160μm以下、140μm以下、或120μm以下。樹脂組成物層之厚度的下限適合為較(C3)成分之平均粒徑dc3(μm)更足夠大，例如可成為dc3+45(μm)以上、dc3+55(μm)以上、dc3+65(μm)以上等。 The thickness of the resin composition layer depends on the application, but from the viewpoint of the heat efficiency diffusion between the layers (conductor layer-insulation layer-conductor layer, semiconductor module-cured material-metal heat radiator, etc.) It is preferably 200 μm or less, more preferably 180 μm or less, still more preferably 160 μm or less, 140 μm or less, or 120 μm or less. The lower limit of the thickness of the resin composition layer is preferably larger than the average particle diameter d c3 (μm) of the (C3) component, and may be, for example, d c3 + 45 (μm) or more, d c3 + 55 (μm) or more, d. C3 +65 (μm) or more.

接著薄膜，例如於有機溶劑調製溶解樹脂組成物之樹脂清漆，將此樹脂清漆使用模塗佈機等塗佈於支持體上，進而使其乾燥，並可藉由形成樹脂組成物層來製造。 Then, the film is, for example, a resin varnish in which a resin composition is dissolved in an organic solvent, and the resin varnish is applied onto a support by a die coater or the like, and further dried, and can be produced by forming a resin composition layer.

作為有機溶劑，例如可列舉丙酮、甲基乙基酮(MEK)及環己酮等之酮類、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之乙酸酯類、溶纖劑及丁基卡必醇等之卡必醇類、甲苯及二 甲苯等之芳香族烴類、二甲基甲醯胺、二甲基乙醯胺(DMAc)及N-甲基吡咯烷酮等之醯胺系溶劑等。有機溶劑可1種單獨使用，亦可組合2種以上使用。 Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether acetate. Acetate such as carbitol acetate, cellosolve, carbitol, butyl carbitol, toluene and An aromatic hydrocarbon such as toluene, a guanamine solvent such as dimethylformamide, dimethylacetamide (DMAc) or N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

乾燥可藉由加熱、吹附熱風等周知之方法實施。乾燥條件雖並未特別限定，但以使樹脂組成物層中之有機溶劑的含量成為10質量%以下，較佳為5質量%以下的方式使其乾燥。雖因樹脂清漆中之有機溶劑的沸點而有所不同，但例如使用包含30質量%~60質量%之有機溶劑的樹脂清漆時，藉由於50℃~150℃使其乾燥3分鐘~10分鐘，可形成樹脂組成物層。 Drying can be carried out by a known method such as heating, blowing hot air or the like. The drying condition is not particularly limited, and the content of the organic solvent in the resin composition layer is preferably 10% by mass or less, preferably 5% by mass or less. Although the resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, for example, when the resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, it is dried for 3 minutes to 10 minutes at 50 ° C to 150 ° C. A resin composition layer can be formed.

本發明者們發現樹脂組成物層之最低熔融黏度為特定的範圍的情況下，得到熱擴散性及對於金屬層之密著強度更為優異之硬化物(絕緣層)。詳細而言，適合樹脂組成物層之最低熔融黏度為500泊~20000泊的範圍。從得到熱擴散性及對於金屬層之密著強度更為優異之硬化物(絕緣層)的觀點來看，樹脂組成物層之最低熔融黏度的下限更佳為5500泊以上，再更佳為6000泊以上、6500泊以上或7000泊以上。又，樹脂組成物層之最低熔融黏度之上限更佳為19000泊以下，再更佳為18000泊以下、17000泊以下、16000泊以下、或15000泊以下。 When the inventors found that the lowest melt viscosity of the resin composition layer is within a specific range, a cured product (insulating layer) having more excellent heat diffusibility and adhesion strength to the metal layer is obtained. Specifically, the lowest melt viscosity of the resin composition layer is in the range of 500 poise to 20,000 poise. The lower limit of the lowest melt viscosity of the resin composition layer is more preferably 5500 poise or more, and still more preferably 6000, from the viewpoint of obtaining a heat-diffusing property and a cured product (insulating layer) which is more excellent in the adhesion strength of the metal layer. Above the parking, more than 6,500 poise or more than 7,000 poise. Further, the upper limit of the minimum melt viscosity of the resin composition layer is more preferably 19,000 poise or less, still more preferably 18,000 poise or less, 17,000 poise or less, 16,000 poise or less, or 15,000 poise or less.

尚，所謂樹脂組成物層之「最低熔融黏度」，係指熔融樹脂組成物層之樹脂時，呈現樹脂組成物層的最低黏度。詳細而言，以一定之昇溫速度加熱樹脂層使樹脂熔融時，初期階段熔融黏度隨溫度上昇一起下降， 然後，超過某溫度時隨溫度上昇，熔融黏度一起上昇。所謂「最低熔融黏度」，係指該斯極小點之熔融黏度。樹脂組成物層之最低熔融黏度可藉由動態黏彈性法測定，例如，可依後述之〔最低熔融黏度之測定〕所記載之方法測定。 In addition, the "lowest melt viscosity" of the resin composition layer means the lowest viscosity of the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin layer is heated at a constant temperature increase rate to melt the resin, the initial stage melt viscosity decreases as the temperature rises. Then, when the temperature rises above a certain temperature, the melt viscosity rises together. The term "minimum melt viscosity" refers to the melt viscosity of the minimum point. The lowest melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method, and can be measured, for example, by the method described in [Measurement of the lowest melt viscosity] described later.

樹脂組成物層之最低熔融黏度，例如可藉由變更(B)成分的含量、(C)成分的含量、(C)成分中之(C1)~(C3)成分之摻合比、樹脂清漆之乾燥條件等來調整。提高無機填充材含量時，樹脂組成物層之最低熔融黏度雖有過度上昇的情況，但於包含組合上述特定之(A)~(C)成分之本發明之樹脂組成物，即使於(C)成分的含量高的情況下，亦得到呈現如上述之適合的最低熔融黏度的樹脂組成物層。 The minimum melt viscosity of the resin composition layer can be changed, for example, by changing the content of the component (B), the content of the component (C), the blending ratio of the components (C1) to (C3) in the component (C), and the resin varnish. Dry conditions, etc. to adjust. When the content of the inorganic filler is increased, the lowest melt viscosity of the resin composition layer is excessively increased, but the resin composition of the present invention containing the specific components (A) to (C) described above is contained in (C). When the content of the component is high, a resin composition layer exhibiting the lowest melt viscosity as described above is also obtained.

在本發明之接著薄膜，於未與樹脂組成物層之支持體接合的面(即，與支持體相反側的面)，可進一步層合依照支持體之保護薄膜。保護薄膜的厚度雖並非特別限定者，但例如為1μm~40μm。藉由層合保護薄膜，可防止對樹脂組成物層的表面之垃圾等之附著或傷痕。接著薄膜可以捲成輥狀進行保存。接著薄膜具有保護薄膜時，藉由剝離保護薄膜變成可使用。 In the adhesive film of the present invention, the protective film according to the support may be further laminated on the surface which is not bonded to the support of the resin composition layer (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion or scratches to the surface of the resin composition layer, such as garbage, can be prevented. The film can then be rolled into a roll for storage. When the film has a protective film, it can be used by peeling off the protective film.

本發明之接著薄膜可適合使用在要求高熱傳導性之用途。亦即，本發明之接著薄膜可適合作為高熱傳導用接著薄膜使用。 The adhesive film of the present invention can be suitably used for applications requiring high thermal conductivity. That is, the adhesive film of the present invention can be suitably used as a film for high heat conduction.

本發明之接著薄膜除了可提供優異之熱擴散 性之外，亦可提供對於金屬層之密著強度優異之硬化物。據此本發明之接著薄膜在功率半導體裝置，可適合使用在半導體模組與金屬放熱體的接著。 The adhesive film of the present invention provides excellent thermal diffusion in addition to In addition to the properties, it is also possible to provide a cured product excellent in adhesion strength to the metal layer. Accordingly, the adhesive film of the present invention can be suitably used in a semiconductor device and a metal heat radiator in a power semiconductor device.

本發明之接著薄膜由於提供熱擴散性及對於金屬層之密著強度雙方皆優異之硬化物(絕緣層)，可適合使用在用以形成印刷配線板之絕緣層(印刷配線板之絕緣層用)，可更適合使用在用以形成印刷配線板之層間絕緣層(印刷配線板之層間絕緣層用)。本發明之接著薄膜，又亦可適合使用在用以嵌入零件內藏電路板之零件(零件嵌入用)。 The adhesive film of the present invention can be suitably used for forming an insulating layer for forming a printed wiring board (an insulating layer for a printed wiring board) by providing a cured product (insulating layer) excellent in thermal diffusibility and adhesion strength to a metal layer. It can be more suitably used for the interlayer insulating layer (for the interlayer insulating layer of the printed wiring board) for forming a printed wiring board. The adhesive film of the present invention can also be suitably used for a part (for component embedding) for embedding a built-in circuit board of a part.

[印刷配線板] [Printed wiring board]

本發明之印刷配線板係包含藉由本發明之樹脂組成物之硬化物所形成的絕緣層。 The printed wiring board of the present invention comprises an insulating layer formed by a cured product of the resin composition of the present invention.

在一實施形態，本發明之印刷配線板使用上述之接著薄膜，可藉由包含下述(I)及(II)之步驟之方法製造。 In one embodiment, the printed wiring board of the present invention can be produced by the method comprising the following steps (I) and (II) using the above-mentioned adhesive film.

(I)於內層基板上，將接著薄膜以該接著薄膜之樹脂組成物層與內層基板接合的方式進行層合之步驟 (I) a step of laminating the adhesive film on the inner substrate in such a manner that the resin composition layer of the adhesive film is bonded to the inner substrate

(II)熱硬化樹脂組成物層以形成絕緣層之步驟 (II) Step of thermosetting the resin composition layer to form an insulating layer

所謂於步驟(I)所使用之「內層基板」，作為主要，係指玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚伸苯基醚基板等之基板、或圖型加工於該基板之單面或兩面而形成導體層 (電路)之電路基板。又製造印刷配線板時，進而應形成絕緣層及/或導體層之中間製造物的內層電路基板亦包含在本發明之所謂「內層基板」。印刷配線板為零件內藏電路板時，使用內藏零件之內層基板即可。 The "inner substrate" used in the step (I) mainly refers to a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether. a substrate or the like, or a pattern formed on one or both sides of the substrate to form a conductor layer (circuit) circuit board. When the printed wiring board is manufactured, the inner layer circuit board in which the intermediate layer of the insulating layer and/or the conductor layer is formed is also included in the so-called "inner substrate" of the present invention. When the printed wiring board is a built-in circuit board for a component, the inner substrate of the built-in component may be used.

內層基板與接著薄膜的層合，例如可藉由從支持體側將接著薄膜加熱壓著在內層基板來進行。作為將接著薄膜加熱壓著在內層基板之構件(以下，亦稱為「加熱壓著構件」)，例如可列舉經加熱之金屬板(SUS鏡板等)或金屬輥(SUS輥)等。尚，較佳為並非將加熱壓著構件直接沖壓在接著薄膜，而是於內層基板之表面凹凸以接著薄膜充分跟隨般，透過耐熱橡膠等之彈性材進行沖壓。 The lamination of the inner layer substrate and the subsequent film can be performed, for example, by heating the adhesive film on the inner layer substrate from the side of the support. As a member for heating the film to the inner layer (hereinafter also referred to as "heating and pressing member"), for example, a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll) may be mentioned. Further, it is preferable that the heating and pressing member is not directly pressed against the film, but the surface of the inner substrate is notched and adhered to the film, and the film is pressed through an elastic material such as heat-resistant rubber.

內層基板與接著薄膜的層合可藉由真空層合法實施。在真空層合法，加熱壓著溫度較佳為60℃~160℃，更佳為80℃~140℃的範圍，加熱壓著壓力較佳為0.098MPa~1.77MPa，更佳為0.29MPa~1.47MPa的範圍，加熱壓著時間較佳為20秒~400秒，更佳為30秒~300秒的範圍。層合較佳為以壓力26.7hPa以下之減壓條件下實施。 The lamination of the inner substrate and the subsequent film can be carried out by vacuum lamination. In the vacuum lamination, the heating and pressing temperature 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 pressing pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa. The range of the heating and pressing time is preferably from 20 seconds to 400 seconds, more preferably from 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure of 26.7 hPa or less.

層合可藉由市售之真空層壓機進行。作為市售之真空層壓機，例如可列舉(股)名機製作所製之真空加壓式層壓機、Nichigo Morton(股)製之真空施加器等。 Lamination can be carried out by a commercially available vacuum laminator. For example, a vacuum press laminator manufactured by Nippon Morika Co., Ltd., a vacuum applicator manufactured by Nichigo Morton Co., Ltd., or the like can be used.

層合之後，常壓下(大氣壓下)，例如藉由 將加熱壓著構件從支持體側進行沖壓，可進行經層合之接著薄膜的平滑化處理。平滑化處理的沖壓條件可成為與上述層合之加熱壓著條件相同之條件。平滑化處理可藉由市售之層壓機進行。尚，層合與平滑化處理可使用上述之市售之真空層壓機連續進行。 After lamination, under normal pressure (at atmospheric pressure), for example by The heating and pressing member is pressed from the side of the support to perform smoothing treatment of the laminated film. The pressing conditions of the smoothing treatment may be the same as the conditions of the heating and pressing of the above-described lamination. The smoothing treatment can be carried out by a commercially available laminating machine. Further, the lamination and smoothing treatment can be carried out continuously using the commercially available vacuum laminator described above.

支持體可於步驟(I)與步驟(II)之間去除，亦可於步驟(II)之後去除。 The support may be removed between step (I) and step (II), or may be removed after step (II).

在步驟(II)，熱硬化樹脂組成物層形成絕緣層。 In the step (II), the thermosetting resin composition layer forms an insulating layer.

樹脂組成物層之熱硬化條件並未特別限定，可使用形成印刷配線板之絕緣層時通常採用之條件。 The thermosetting condition of the resin composition layer is not particularly limited, and conditions generally employed in forming an insulating layer of a printed wiring board can be used.

例如，樹脂組成物層之熱硬化條件雖因樹脂組成物之種類等而不同，但硬化溫度可成為120℃~240℃的範圍(較佳為150℃~220℃的範圍，更佳為170℃~200℃的範圍)，硬化時間可成為5分鐘~120分鐘的範圍(較佳為10分鐘~100分鐘，更佳為15分鐘~90分鐘)。 For example, the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, etc., but the curing temperature may be in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably 170 ° C). In the range of ~200 ° C), the hardening time may be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

使樹脂組成物層熱硬化之前，可將樹脂組成物層在較硬化溫度更低之溫度進行預備加熱。例如使樹脂組成物層熱硬化之前，在50℃以上未滿120℃(較佳為60℃以上且110℃以下，更佳為70℃以上且100℃以下)的溫度，可預備加熱樹脂組成物層5分鐘以上(較佳為5分鐘~150分鐘，更佳為15分鐘~120分鐘)。 The resin composition layer may be preheated at a temperature lower than the hardening temperature before the resin composition layer is thermally cured. For example, before the thermosetting of the resin composition layer, the resin composition can be prepared to be heated at a temperature of 50 ° C or more and less than 120 ° C (preferably 60 ° C or more and 110 ° C or less, more preferably 70 ° C or more and 100 ° C or less). The layer is more than 5 minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

藉由本發明之樹脂組成物的硬化物所形成之 絕緣層可表現充分之熱擴散性。例如，絕緣層雖因所使用之樹脂組成物中之無機填充材的含量及種類而不同，但可表現較佳為8W/m．K以上，更佳為8.2W/m．K以上，再更佳為8.4W/m．K以上、8.5W/m．K以上、8.6W/m．K以上、8.7W/m．K以上、8.8W/m．K以上、8.9W/m．K以上、或9.0W/m．K以上的熱傳導。本發明之絕緣層之熱傳導率之上限雖並未特別限定，但通常為30W/m．K以下。絕緣層之熱傳導率，例如可藉由熱流計法及溫度波分析法等周知之方法測定。在本發明，絕緣層之熱傳導率可依後述之〔硬化物之熱傳導率之測定〕的記載來測定。 Formed by the cured product of the resin composition of the present invention The insulating layer can exhibit sufficient thermal diffusivity. For example, although the insulating layer differs depending on the content and type of the inorganic filler in the resin composition used, it can preferably exhibit 8 W/m. Above K, more preferably 8.2W/m. Above K, more preferably 8.4W/m. K or more, 8.5W/m. K or more, 8.6W/m. K or more, 8.7W/m. K or more, 8.8W/m. K or above, 8.9W/m. K or above, or 9.0W/m. Heat conduction above K. The upper limit of the thermal conductivity of the insulating layer of the present invention is not particularly limited, but is usually 30 W/m. Below K. The thermal conductivity of the insulating layer can be measured, for example, by a known method such as a heat flow meter method or a temperature wave analysis method. In the present invention, the thermal conductivity of the insulating layer can be measured by the description of the measurement of the thermal conductivity of the cured product described later.

製造印刷配線板時，可進一步實施(III)鑽孔在絕緣層之步驟、(IV)粗糙化處理絕緣層之步驟、(V)形成導體層之步驟。此等之步驟(III)~(V)，可依使用在印刷配線板之製造，對本發明領域具有通過知識者而言係周知之各種方法來實施。尚，將支持體於步驟(II)之後去除的情況下，該支持體的去除可於步驟(II)與步驟(III)之間、步驟(III)與步驟(IV)之間、或步驟(IV)與步驟(V)之間實施。 When the printed wiring board is manufactured, the steps of (III) drilling the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer may be further performed. These steps (III) to (V) can be carried out by various methods well known to those skilled in the art in the field of the present invention, depending on the use of the printed wiring board. Further, in the case where the support is removed after the step (II), the removal of the support may be between the step (II) and the step (III), between the step (III) and the step (IV), or the step ( Implemented between IV) and step (V).

步驟(III)係鑽孔在絕緣層之步驟，藉此可於絕緣層形成通孔、貫穿孔等之孔。步驟(III)係因應使用在絕緣層之形成之樹脂組成物的組成等，例如可使用鑽孔、雷射、電漿等來實施。孔之尺寸或形狀可因應印刷配線板之設計適當決定。 The step (III) is a step of drilling a hole in the insulating layer, whereby a hole of a through hole, a through hole or the like can be formed in the insulating layer. The step (III) is carried out by, for example, drilling, laser, plasma, or the like in accordance with the composition of the resin composition formed in the insulating layer. The size or shape of the holes can be appropriately determined in accordance with the design of the printed wiring board.

步驟(IV)係粗糙化處理絕緣層之步驟。粗糙化處理 的順序、條件並未特別限定，可採用形成印刷配線板之絕緣層時通常所使用之周知順序、條件。例如，可依藉由膨潤液之膨潤處理、藉由氧化劑之粗糙化處理、藉由中和液之中和處理的順序來實施，粗糙化處理絕緣層。作為膨潤液雖並未特別限定，但可列舉鹼溶液、界面活性劑溶液等，較佳為鹼溶液，作為該鹼溶液，更佳為氫氧化鈉溶液、氫氧化鉀溶液。作為市售之膨潤液，例如可列舉Atotech Japan(股)製之「Swelling Dip Securiganth P」、「Swelling Dip Securiganth SBU」等。藉由膨潤液之膨潤處理雖並未特別限定，但例如可藉由於30℃~90℃之膨潤液浸漬絕緣層1分鐘~20分鐘來進行。從將絕緣層之樹脂的膨潤抑制在適度水準的觀點來看，較佳為於40℃~80℃之膨潤液使硬化體浸漬5分鐘~15分鐘。作為氧化劑，雖並未特別限定，但例如可列舉溶解過錳酸鉀或過錳酸鈉於氫氧化鈉之水溶液的鹼性過錳酸溶液。藉由鹼性過錳酸溶液等之氧化劑的粗糙化處理，較佳為於加熱至60℃~80℃之氧化劑溶液使絕緣層浸漬10分鐘~30分鐘來進行。又，較佳為在鹼性過錳酸溶液之過錳酸鹽的濃度為5質量%~10質量%。作為市售之氧化劑，例如可列舉Atotech Japan(股)製之「Concentrate Compact CP」、「Dosingsolution Securiganth P」等之鹼性過錳酸溶液。又，作為中和液，較佳為酸性之水溶液，作為市售品，例如可列舉Atotech Japan(股)製之「Reductionsolution Securiganth P」。藉由中和液之處理 可藉由將未經藉由氧化劑之粗糙化處理的處理面於30℃~80℃之中和液浸漬5分鐘~30分鐘來進行。從作業性等之點，較佳為將未經藉由氧化劑之粗糙化處理的對象物於40℃~70℃之中和液浸漬5分鐘~20分鐘的方法。 Step (IV) is a step of roughening the insulating layer. Roughening The order and conditions are not particularly limited, and a well-known sequence and conditions which are generally used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer may be roughened by a swelling treatment of the swelling liquid, a roughening treatment by an oxidizing agent, and a neutralization treatment by a neutralizing liquid. The swelling solution is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, and an alkali solution is preferred. The alkali solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of the commercially available swelling liquid include "Swelling Dip Securiganth P" manufactured by Atotech Japan Co., Ltd., "Swelling Dip Securiganth SBU", and the like. The swelling treatment by the swelling liquid is not particularly limited. For example, the insulating layer may be immersed in a swelling liquid at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred that the hardened body is immersed in a swelling liquid at 40 ° C to 80 ° C for 5 minutes to 15 minutes. The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganic acid solution in which an aqueous solution of potassium permanganate or sodium permanganate in sodium hydroxide is dissolved. The roughening treatment of the oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. The commercially available oxidizing agent is, for example, an alkaline permanganic acid solution such as "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd. or "Dosingsolution Securiganth P". In addition, as the neutralizing liquid, an acidic aqueous solution is preferable, and as a commercial item, for example, "Reductionsolution Securiganth P" manufactured by Atotech Japan Co., Ltd. is mentioned. Treatment with neutralizing liquid This can be carried out by immersing the treated surface which has not been subjected to the roughening treatment with an oxidizing agent at 30 ° C to 80 ° C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method in which an object which has not been subjected to roughening treatment by an oxidizing agent is immersed in a liquid at 40 ° C to 70 ° C for 5 minutes to 20 minutes is preferred.

在一實施形態，粗糙化處理後之絕緣層表面的算術平均粗糙度Ra較佳為500nm以下，更佳為400nm以下，再更佳為350nm以下，又再更佳為300nm以下、250nm以下、200nm以下、150nm以下、或100nm以下。絕緣層表面的算術平均粗糙度(Ra)可使用非接觸型表面粗糙度計測定。作為非接觸型表面粗糙度計之具體例，可列舉威科儀器公司製之「WYKO NT3300」。 In one embodiment, the arithmetic mean roughness Ra of the surface of the insulating layer after the roughening treatment is preferably 500 nm or less, more preferably 400 nm or less, still more preferably 350 nm or less, and still more preferably 300 nm or less, 250 nm or less, or 200 nm. Hereinafter, it is 150 nm or less, or 100 nm or less. The arithmetic mean roughness (Ra) of the surface of the insulating layer can be measured using a non-contact type surface roughness meter. Specific examples of the non-contact surface roughness meter include "WYKO NT3300" manufactured by Wyco Instruments.

步驟(V)係形成導體層之步驟。 Step (V) is a step of forming a conductor layer.

在印刷配線板，使用在導體層之導體材料並未特別限定。於適合之實施形態，導體層係包商選擇自由金、鉑、鈀、銀、銅、鋁、鈷、鉻、鋅、鎳、鈦、鎢、鐵、錫及銦所構成之群組中之1種以上的金屬。導體層可為單金屬層亦可為合金層，作為合金層，例如可列舉由選擇自上述之群組中之2種以上金屬的合金(例如鎳．鉻合金、銅．鎳合金及銅．鈦合金)所形成之層。其中，從導體層形成之通用性、成本、圖型化之容易性等之觀點來看，較佳鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅之單金屬層、或鎳．鉻合金、銅．鎳合金、銅．鈦合金之合金層，更佳為鉻、鎳、鈦、鋁、鋅、金、鈀、銀或銅之單金屬層、或鎳．鉻合金之合金層，再更佳為鋁或銅之單金屬層。導體層 可為單層結構，亦可為由不同種類之金屬或合金所構成之單金屬層或層合2層以上合金層之複層結構。導體層為複層結構時，與絕緣層接觸之層，較佳為鉻、鋅或鈦之單金屬層、或鎳．鉻合金之合金層。 In the printed wiring board, the conductor material used in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer is selected from the group consisting of free gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. More than one kind of metal. The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include alloys selected from the group consisting of two or more metals (for example, nickel, chromium alloy, copper, nickel alloy, copper, titanium). The layer formed by the alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel is preferable from the viewpoints of versatility, cost, ease of pattern formation, and the like of the formation of the conductor layer. . Chrome alloy, copper. Nickel alloy, copper. The alloy layer of titanium alloy is more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel. The alloy layer of chrome alloy is more preferably a single metal layer of aluminum or copper. Conductor layer It may be a single layer structure, or may be a single metal layer composed of different kinds of metals or alloys or a laminated structure of two or more alloy layers laminated. When the conductor layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or nickel. Alloy layer of chrome alloy.

導體層之厚度雖視所期望之印刷配線板的設計而定，但一般為3μm~35μm，較佳為5μm~30μm。 The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

在使用本發明之樹脂組成物所製造之本發明之印刷配線板，絕緣層對於導體層(金屬層)顯示良好之密著強度。詳細而言在本發明之印刷配線板，絕緣層與導體層的密著強度較佳可成為0.5kgf/cm以上，更佳為0.55kgf/cm以上，再更佳為0.6kgf/cm以上、0.62kgf/cm以上、0.64kgf/cm以上、0.66kgf/cm以上、0.68kgf/cm以上、或0.7kgf/cm以上。該密著強度之上限雖並未特別限定，但通常成為1.0kgf/cm以下、0.9kgf/cm以下等。在本發明之印刷配線板，絕緣層呈現優異之熱擴散性，同時對於如此之導體層呈現高密著強度。據此，在安裝半導體元件於該印刷配線板而成之半導體裝置，半導體元件所產生的熱可通過印刷配線板全體更有效率擴散。尚，所謂絕緣層與導體層的剝離強度，係指將導體層對於絕緣層以垂直方向(90度方向)剝離時之剝離強度(90度剝離(Peel)強度)，可藉由將導體層對於絕緣層以垂直方向(90度方向)剝離時之剝離強度以拉伸試驗機測定求得。作為拉伸試驗機，例如可列舉(股)TSE製之「AC-50C-SL」等。 In the printed wiring board of the present invention produced by using the resin composition of the present invention, the insulating layer exhibits good adhesion strength to the conductor layer (metal layer). Specifically, in the printed wiring board of the present invention, the adhesion strength between the insulating layer and the conductor layer is preferably 0.5 kgf/cm or more, more preferably 0.55 kgf/cm or more, still more preferably 0.6 kgf/cm or more and 0.62. Kgf/cm or more, 0.64 kgf/cm or more, 0.66 kgf/cm or more, 0.68 kgf/cm or more, or 0.7 kgf/cm or more. The upper limit of the adhesion strength is not particularly limited, but is usually 1.0 kgf/cm or less and 0.9 kgf/cm or less. In the printed wiring board of the present invention, the insulating layer exhibits excellent thermal diffusibility while exhibiting high adhesion strength to such a conductor layer. According to this, in the semiconductor device in which the semiconductor element is mounted on the printed wiring board, the heat generated by the semiconductor element can be more efficiently diffused by the entire printed wiring board. In addition, the peeling strength of the insulating layer and the conductor layer refers to the peeling strength (90-degree peeling strength) when the conductor layer is peeled off in the vertical direction (90-degree direction) of the insulating layer, and the conductor layer can be The peel strength when the insulating layer was peeled off in the vertical direction (90-degree direction) was determined by a tensile tester. Examples of the tensile tester include "AC-50C-SL" manufactured by TSE.

使用本發明之印刷配線板，可製造半導體裝置。 A semiconductor device can be manufactured using the printed wiring board of the present invention.

作為半導體裝置，可列舉供於電氣製品(例如電腦、手機、數位相機及電視等)及車輛(例如摩托車、汽車、電車、船舶及航空機等)等之各種半導體裝置。 Examples of the semiconductor device include various semiconductor devices such as electric products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, electric cars, ships, and aircraft).

本發明之半導體裝置可藉由於印刷配線板之傳導點，安裝半導體元件來製造。所謂「傳導點」，係「傳遞在印刷配線板之電氣信號的點」，其地點可為表面，亦可為嵌入地點皆無妨。又，若半導體元件係將半導體作為材料之電氣電路元件則並未特別限定。 The semiconductor device of the present invention can be fabricated by mounting a semiconductor element due to the conduction point of the printed wiring board. The "conducting point" is a "point of electrical signal transmitted to a printed wiring board", and the location can be either a surface or an embedding location. Further, the semiconductor element is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

製造本發明之半導體裝置時之半導體元件的安裝方法，若半導體元件能有效功能，雖並未特別限定，但具體而言，可列舉引線接合安裝方法、倒裝芯片安裝方法、藉由內建非凹凸層(bumpless build up layer)(BBUL)之安裝方法、藉由各向異性導電薄膜(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「藉由內建非凹凸層(BBUL)之安裝方法」，係指「將半導體元件直接嵌入印刷配線板之凹部，使半導體元件與印刷配線板上之電路配線連接之安裝方法」。 The method of mounting the semiconductor device in the manufacture of the semiconductor device of the present invention is not particularly limited as long as the semiconductor device can function effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and a built-in non- A method of mounting a bumpless build up layer (BBUL), a method of mounting an anisotropic conductive film (ACF), a method of mounting a non-conductive film (NCF), and the like. Here, the "mounting method by the built-in non-concave-convex layer (BBUL)" means a method of mounting a semiconductor element directly in a concave portion of a printed wiring board to connect a semiconductor element to a circuit wiring on a printed wiring board. .

[功率半導體裝置] [Power semiconductor device]

半導體元件當中，電力用半導體元件(功率半導體元 件)發熱量特別大。如先述，本發明之樹脂組成物係提供熱擴散性及對於金屬層之密著強度雙方皆優異之硬化物。據此，本發明之樹脂組成物在安裝功率半導體元件之半導體裝置(功率半導體裝置)，為了形成熱擴散層可有利地使用。 Among semiconductor components, power semiconductor components (power semiconductor elements) Pieces) The heat is particularly large. As described above, the resin composition of the present invention provides a cured product excellent in both heat diffusibility and adhesion strength to a metal layer. Accordingly, the resin composition of the present invention can be advantageously used in order to form a thermal diffusion layer in a semiconductor device (power semiconductor device) on which a power semiconductor element is mounted.

以下，表示將藉由本發明之樹脂組成物的硬化物所形成之絕緣層作為熱擴散層包含之功率半導體裝置之一例。 Hereinafter, an example of a power semiconductor device including the insulating layer formed of the cured product of the resin composition of the present invention as a thermal diffusion layer will be described.

在一實施形態，本發明之功率半導體裝置係包含具有第1及第2主面之金屬放熱體、具有第1及第2主面之半導體模組、及絕緣層，該絕緣層係以金屬放熱體之第1主面與半導體模組之第2主面接合的方式，藉由設置於金屬放熱體與半導體模組之間的本發明之樹脂組成物的硬化物而形成。 In one embodiment, the power semiconductor device of the present invention includes a metal heat sink having first and second main faces, a semiconductor module having first and second main faces, and an insulating layer, wherein the insulating layer is heated by a metal The first main surface of the body is bonded to the second main surface of the semiconductor module, and is formed by a cured product of the resin composition of the present invention provided between the metal heat radiator and the semiconductor module.

於圖1係表示有關上述實施形態之本發明之功率半導體裝置的模式圖(省略與外部電路的配線)。在圖1，功率半導體裝置10係包含金屬放熱體1、半導體模組3、及藉由設置在金屬放熱體1與半導體模組3之間的本發明之樹脂組成物的硬化物所形成之絕緣層2。 Fig. 1 is a schematic view showing a power semiconductor device according to the above-described embodiment of the present invention (the wiring of the external circuit is omitted). In FIG. 1, a power semiconductor device 10 includes a metal heat radiator 1, a semiconductor module 3, and an insulating layer formed by a cured product of the resin composition of the present invention disposed between the metal heat radiator 1 and the semiconductor module 3. Layer 2.

金屬放熱體1係具有第1主面1a與第2主面1b。金屬放熱體若為由金屬材料所構成之放熱體則並未特別限定，可使用在功率半導體裝置可使用之周知的金屬放熱體。作為金屬放熱體之金屬材料，適合為鋁、銅。 The metal heat radiator 1 has a first main surface 1a and a second main surface 1b. The metal heat radiator is not particularly limited as long as it is composed of a metal material, and a well-known metal heat radiator which can be used in a power semiconductor device can be used. As the metal material of the metal heat radiator, aluminum or copper is suitable.

金屬放熱體1之第1主面1a可為平坦亦可為凹凸。本發明之樹脂組成物即使金屬放熱體之第1主面1a平坦，亦可實現對於該金屬放熱體呈現良好之密著強度的硬化物(絕緣層)。例如，金屬放熱體之第1主面的算術平均粗糙度(Ra)可為500nm以下、400nm以下、300nm以下、200nm以下、100nm以下、或50nm以下。金屬放熱體之第1主面之Ra的下限雖並未特別限定，但從使絕緣層與金屬放熱體的密著強度穩定化的觀點來看，較佳可成為1nm以上、5nm以上、10nm以上等。 The first main surface 1a of the metal heat radiator 1 may be flat or irregular. In the resin composition of the present invention, even if the first main surface 1a of the metal heat radiator is flat, a cured product (insulating layer) exhibiting good adhesion strength to the metal heat radiator can be realized. For example, the arithmetic mean roughness (Ra) of the first main surface of the metal heat radiator may be 500 nm or less, 400 nm or less, 300 nm or less, 200 nm or less, 100 nm or less, or 50 nm or less. The lower limit of Ra of the first main surface of the metal heat radiator is not particularly limited, but from the viewpoint of stabilizing the adhesion strength between the insulating layer and the metal heat radiator, it is preferably 1 nm or more, 5 nm or more, or 10 nm or more. Wait.

金屬放熱體1之第2主面1b可為平坦亦可為凹凸。從於外部環境有效率使熱擴散的觀點來看，金屬放熱體之第2主面適合以放熱表面積增大的方式具有凹凸形狀(未圖示)。 The second main surface 1b of the metal heat radiator 1 may be flat or uneven. The second main surface of the metal heat radiator is preferably provided with a concavo-convex shape (not shown) so that the surface area of the heat radiating surface increases from the viewpoint of efficient heat dissipation in the external environment.

金屬放熱體1可有效率擴散來自半導體模組3的熱的方式，可於內部形成熱交換媒體(例如水等之冷媒)的流路(未圖示)。 The metal heat radiator 1 can efficiently diffuse heat from the semiconductor module 3, and a flow path (not shown) of a heat exchange medium (for example, a refrigerant such as water) can be formed inside.

在圖1所示之實施形態，半導體模組3係包含半導體元件基板4、功率半導體元件8、及用以使半導體元件基板與功率半導體元件傳導之導線9。半導體元件基板4係包含基板6、與設置在該基板之絕緣層2側的表面之金屬層7、與設置在和該基板之絕緣層2相反側的表面之金屬層(電路)5。基板6可與在上述[印刷配線板]之「內層基板」相同，可從本發明之樹脂組成物之硬化物形成。金屬層(電路)5及金屬層6可與在上述[印刷配線 板]之「導體層」相同。半導體元件基板4，又可為包含藉由本發明之樹脂組成物的硬化物所形成之絕緣層的印刷配線板。在本發明之功率半導體裝置，半導體模組並非被限定於圖1所記載之實施形態者，若為包含功率半導體元件之半導體模組則並未特別限定可使用。例如，如日本特開2002-246542號公報所記載之功率半導體裝置般，可使用包含引線框架、與安裝在該引線框架之功率半導體元件的半導體模組。 In the embodiment shown in FIG. 1, the semiconductor module 3 includes a semiconductor element substrate 4, a power semiconductor element 8, and a wire 9 for conducting the semiconductor element substrate and the power semiconductor element. The semiconductor element substrate 4 includes a substrate 6, a metal layer 7 provided on the surface of the insulating layer 2 side of the substrate, and a metal layer (circuit) 5 provided on the surface opposite to the insulating layer 2 of the substrate. The substrate 6 can be formed from the cured product of the resin composition of the present invention in the same manner as the "inner substrate" of the above [printed wiring board]. The metal layer (circuit) 5 and the metal layer 6 can be combined with the above [printed wiring The "conductor layer" of the board is the same. The semiconductor element substrate 4 may be a printed wiring board including an insulating layer formed of a cured product of the resin composition of the present invention. In the power semiconductor device of the present invention, the semiconductor module is not limited to the embodiment described in FIG. 1, and the semiconductor module including the power semiconductor device is not particularly limited. For example, a semiconductor module including a lead frame and a power semiconductor element mounted on the lead frame can be used as in the power semiconductor device described in Japanese Laid-Open Patent Publication No. 2002-246542.

藉由本發明之樹脂組成物的硬化物所形成之絕緣層2，由於提供對於金屬層之密著強度良好之硬化物，即使半導體模組之第2主面3b(亦即金屬層7之表面)平坦，可實現對於該半導體模組良好之密著強度。半導體模組之第2主面的Ra可為與金屬放熱體之第1主面的Ra相同。 The insulating layer 2 formed by the cured product of the resin composition of the present invention provides a cured product having good adhesion strength to the metal layer even if the second main surface 3b of the semiconductor module (that is, the surface of the metal layer 7) Flatness can achieve good adhesion strength to the semiconductor module. The Ra of the second main surface of the semiconductor module may be the same as Ra of the first main surface of the metal heat radiator.

據此在一實施形態，金屬放熱體之第1主面及半導體模組之第2主面之至少一者的Ra可為500nm以下。 According to this embodiment, at least one of the first main surface of the metal heat radiator and the second main surface of the semiconductor module may have a Ra of 500 nm or less.

藉由本發明之樹脂組成物的硬化物所形成之絕緣層係熱擴散性及對於金屬層之密著強度雙方皆優異。在一實施形態，絕緣層之熱傳導率為8W/m．K以上，絕緣層與金屬放熱體之第1主面及半導體模組之第2主面之至少一者的密著強度為0.5kgf/cm以上。尚，絕緣層之熱傳導率的適合範圍係如針對上述[印刷配線板]之絕緣層所記載，又，絕緣層與金屬放熱體之第1主面及半導體模組之 第2主面之至少一者的密著強度，可與上述[印刷配線板]之絕緣層與導體層的密著強度相同。 The insulating layer formed by the cured product of the resin composition of the present invention is excellent in both thermal diffusibility and adhesion strength to the metal layer. In one embodiment, the thermal conductivity of the insulating layer is 8 W/m. K or more, the adhesion strength between the insulating layer and at least one of the first main surface of the metal heat radiator and the second main surface of the semiconductor module is 0.5 kgf/cm or more. Further, the suitable range of the thermal conductivity of the insulating layer is as described for the insulating layer of the above [printed wiring board], and the first main surface of the insulating layer and the metal heat releasing body and the semiconductor module The adhesion strength of at least one of the second main faces may be the same as the adhesion strength between the insulating layer and the conductor layer of the above [printed wiring board].

在本發明之功率半導體裝置，功率半導體元件由於因光或熱、濕度等環境所導致之劣化故應保護，可設置密封半導體模組之密封樹脂(未圖示)。密封樹脂可使用在半導體裝置之製造可使用之周知的樹脂，可使用本發明之樹脂組成物。據此，在一實施形態，本發明之功率半導體裝置係具備藉由密封半導體模組的方式所設置之本發明之樹脂組成物的硬化物所形成之密封層。 In the power semiconductor device of the present invention, the power semiconductor element should be protected from deterioration due to light, heat, humidity, or the like, and a sealing resin (not shown) for sealing the semiconductor module can be provided. As the sealing resin, a well-known resin which can be used for the manufacture of a semiconductor device can be used, and the resin composition of the present invention can be used. According to this embodiment, the power semiconductor device of the present invention includes the sealing layer formed of the cured product of the resin composition of the present invention provided by sealing the semiconductor module.

[層合體] [Layer]

本發明又提供絕緣層與金屬層之層合體。 The invention further provides a laminate of an insulating layer and a metal layer.

以往，絕緣層之熱擴散性係與對於金屬層之密著強度有權衡關係，不存在熱擴散性及對於金屬層之密著強度雙方皆優異之絕緣層。 Conventionally, the thermal diffusivity of the insulating layer has a trade-off relationship with respect to the adhesion strength to the metal layer, and there is no insulating layer excellent in both thermal diffusibility and adhesion strength to the metal layer.

本發明之層合體係絕緣層與金屬層之層合體，其特徵為絕緣層之熱傳導率為8W/m．K以上，且絕緣層與金屬層的密著強度為0.5kgf/cm以上。 The laminate of the insulating layer and the metal layer of the laminated system of the present invention is characterized in that the thermal conductivity of the insulating layer is 8 W/m. K or more, and the adhesion strength between the insulating layer and the metal layer is 0.5 kgf/cm or more.

包含熱擴散性及對於金屬層之密著強度雙方皆優異之絕緣層的本發明之層合體，係初次使用本發明之樹脂組成物而實現者。亦即，本發明之層合體係包含藉由本發明之樹脂組成物的硬化物所形成之絕緣層與金屬層。絕緣層之熱傳導率的合適範圍以及絕緣層與金屬層的密著強度之合適範圍係如上述[印刷配線板]所記載。 The laminate of the present invention comprising an insulating layer excellent in thermal diffusibility and adhesion strength to both metal layers is realized by using the resin composition of the present invention for the first time. That is, the laminate system of the present invention comprises an insulating layer and a metal layer formed by the cured product of the resin composition of the present invention. A suitable range of the thermal conductivity of the insulating layer and a suitable range of the adhesion strength between the insulating layer and the metal layer are as described in the above [Printed Wiring Board].

在本發明之層合體，金屬層之與絕緣層接合之表面的算術平均粗糙度(Ra)可為500nm以下、400nm以下、300nm以下、200nm以下、100nm以下、或50nm以下。該Ra之下限雖並未特別限定，但從使絕緣層與金屬層的密著強度穩定化的觀點來看，較佳可成為1nm以上、5nm以上、10nm以上等。據此，在一實施形態，金屬層之與絕緣層接合之表面的Ra為500nm以下。在本發明之層合體，如此即使是金屬層之表面的Ra低的情況，絕緣層與金屬層亦可呈現良好之密著強度。 In the laminate of the present invention, the arithmetic mean roughness (Ra) of the surface of the metal layer joined to the insulating layer may be 500 nm or less, 400 nm or less, 300 nm or less, 200 nm or less, 100 nm or less, or 50 nm or less. The lower limit of Ra is not particularly limited, but from the viewpoint of stabilizing the adhesion strength between the insulating layer and the metal layer, it is preferably 1 nm or more, 5 nm or more, 10 nm or more. Accordingly, in one embodiment, the Ra of the surface of the metal layer bonded to the insulating layer is 500 nm or less. In the laminate of the present invention, even when the Ra of the surface of the metal layer is low, the insulating layer and the metal layer can exhibit good adhesion strength.

在本發明之層合體，金屬層可與在上述[印刷配線板]之「導體層」相同。金屬層，又可與在上述[功率半導體裝置]之「金屬放熱體」相同。據此，在本發明之層合體，金屬層適合為由銅或鋁所構成。 In the laminate of the present invention, the metal layer can be the same as the "conductor layer" of the above [printed wiring board]. The metal layer may be the same as the "metal heat radiator" of the above [Power Semiconductor Device]. Accordingly, in the laminate of the present invention, the metal layer is suitably composed of copper or aluminum.

尚，在本發明之印刷配線板、功率半導體裝置、及層合體，絕緣層之厚度可與在[接著薄膜]之樹脂組成物層之適合厚度相同。使用本發明之接著薄膜形成絕緣層的情況下，如有必要可使用複數之接著薄膜，層合樹脂組成物層彼此以達成所期望厚度的絕緣層。 Further, in the printed wiring board, the power semiconductor device, and the laminate of the present invention, the thickness of the insulating layer may be the same as the thickness of the resin composition layer of the [following film]. In the case of forming an insulating layer using the adhesive film of the present invention, if necessary, a plurality of adhesive films may be used, and the resin composition layers may be laminated to each other to achieve an insulating layer having a desired thickness.

[實施例] [Examples]

以下，雖將本發明藉由實施例進行具體說明，但本發明並非被限定於此等之實施例。尚，在以下之記載，「份」及「%」除非另有說明，分別意味著「質量份」及「質量%」。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. In the following, "parts" and "%" mean "parts by mass" and "% by mass" unless otherwise stated.

<測定方法．評估方法> <Measurement method. Evaluation method>

首先針對各種測定方法．評估方法進行說明。 First of all, for various measurement methods. The evaluation method is explained.

〔測定．評估用基板之調製〕 [Measurement. Modulation of the substrate for evaluation]

將於實施例及比較例製作之接著薄膜使用高溫真空沖壓裝置(北川精機(股)製「KVHC-PRESS」)，以樹脂組成物層與鋁板接合的方式，層合於鋁板((股)金屬切割製之5052-H32材)。層合係藉由進行減壓使氣壓成為13hPa以下後，以120℃、壓力3kgf/cm2沖壓5分鐘來進行。然後，剝離支持體，於經露出之樹脂組成物層的表面，以接合樹脂組成物層與電解銅箔的光澤面的方式，來層合電解銅箔(JX日鑛日石金屬(股)製「JTCP-35u」、光澤面之Ra：200nm)。其次，使用上述高溫真空沖壓裝置，進行減壓使氣壓成為13hPa以下之後，以140℃、壓力5kgf/cm210分鐘，其次以200℃、壓力5kgf/cm290分鐘進行沖壓，使樹脂組成物層硬化而形成絕緣層。 The film produced in the examples and the comparative examples was laminated on an aluminum plate by using a high-temperature vacuum press ("KVHC-PRESS" manufactured by Kitagawa Seiki Co., Ltd.) in a manner of bonding the resin composition layer to the aluminum plate. Cut the 5052-H32 material). The laminating system was carried out by pressing at a pressure of 3 kgf/cm 2 at 120 ° C for 5 minutes after the pressure was reduced to 13 hPa or less. Then, the support is peeled off, and the electrolytic copper foil (JX Nippon Mining & Metal Co., Ltd.) is laminated on the surface of the exposed resin composition layer so as to bond the resin composition layer and the shiny surface of the electrolytic copper foil. "JTCP-35u", Ra of glossy surface: 200 nm). Next, using the high-temperature vacuum press apparatus described above, the pressure was reduced to 13 hPa or less, and then pressurized at 140 ° C, a pressure of 5 kgf/cm 2 for 10 minutes, and then at 200 ° C and a pressure of 5 kgf/cm 2 for 90 minutes to form a resin composition. The layer is hardened to form an insulating layer.

〔密著強度之測定〕 [Measurement of adhesion strength]

於測定．評估用基板之銅箔，放入寬度10mm、長度50mm之部分的切口部，剝離此一端再以挾具((股)DSI製之Auto com型試驗機「AC-50C-SL」)挾住，在室溫中以50mm/分鐘之速度於垂直方向，測定剝離10mm時 之荷重(kgf/cm)，求得密著強度。 For measurement. The copper foil of the evaluation substrate was placed in a notched portion having a width of 10 mm and a length of 50 mm, and the end was peeled off, and then the end was peeled off by a cookware ("Auto-50"-type "AC-50C-SL" manufactured by DSI). In the vertical direction at a rate of 50 mm/min at room temperature, when peeling 10 mm was measured The load (kgf/cm) is used to obtain the adhesion strength.

〔硬化物之熱傳導率的測定〕 [Measurement of Thermal Conductivity of Hardened Materials] (1)硬化物試料的調製 (1) Modification of hardened sample

將於實施例及比較例製作之接著薄膜，於140℃加熱10分鐘後，剝離支持體。將如此所得之樹脂組成物層重疊5片後，以200℃、壓力20kgf/cm2沖壓90分鐘使樹脂組成物層硬化，而得到硬化物試料。 The film prepared in the examples and the comparative examples was heated at 140 ° C for 10 minutes, and then the support was peeled off. After the resin composition layer thus obtained was laminated in five sheets, the resin composition layer was cured by pressing at 200 ° C and a pressure of 20 kgf/cm 2 for 90 minutes to obtain a cured sample.

(2)熱擴散率α之測定 (2) Determination of thermal diffusivity α

針對硬化物試料，將該硬化物之厚度方向的熱擴散率α(m2/s)使用ai-Phase公司製「ai-Phase Mobile 1u」，由溫度波分析法測定。針對同一試料進行3次測定，算出平均值。 For the cured sample, the thermal diffusivity α (m 2 /s) in the thickness direction of the cured product was measured by a temperature wave analysis method using "ai-Phase Mobile 1u" manufactured by ai-Phase Co., Ltd. Three measurements were performed on the same sample, and the average value was calculated.

(3)比熱容量Cp之測定 (3) Determination of specific heat capacity Cp

針對硬化物試料，使用示差掃描熱量計(SII奈米技術(股)製「DSC7020」)，從-40℃至80℃以10℃/分鐘進行昇溫，藉由測定，算出該硬化物試料於20℃之比熱容量Cp(J/kg．K)。 For the cured sample, a differential scanning calorimeter ("DSC7020" manufactured by SII Nanotechnology Co., Ltd.) was used, and the temperature was raised from -40 ° C to 80 ° C at 10 ° C / min, and the cured sample was calculated by measurement. The specific heat capacity of °C is Cp (J/kg.K).

(4)密度ρ之測定 (4) Determination of density ρ

將硬化物試料之密度(kg/m3)使用梅特勒-托利多(股)製分析天秤XP105(使用比重測定套件)測定。 The density (kg/m 3 ) of the cured sample was measured using a METTLER TOLEDO analytical scale Libra XP105 (using a specific gravity measuring kit).

(5)熱傳導率λ的算出 (5) Calculation of thermal conductivity λ

將於上述(2)~(4)所得之熱擴散率α(m2/s)、比熱容量Cp(J/kg．K)、及密度ρ(kg/m3)代入述式(I)，算出熱傳導率λ(W/m．K)。 The thermal diffusivity α (m 2 /s), the specific heat capacity Cp (J/kg.K), and the density ρ (kg/m 3 ) obtained in the above (2) to (4) are substituted into the formula (I). The thermal conductivity λ (W/m.K) was calculated.

λ=α×Cp×ρ (I) λ=α×Cp× ρ (I)

〔最低熔融黏度之測定〕 [Measurement of the lowest melt viscosity]

針對於實施例及比較例製作之接著薄膜的樹脂組成物層，使用動態黏彈性測定裝置((股)UBM製「Rheosol-G3000」)，測定熔融黏度。針對試料樹脂組成物1.8g，使用直徑18mm之平行板，從測定開始溫度60℃在昇溫速度5℃/分鐘進行昇溫，在測定溫度間隔2.5℃、振動數1Hz、扭曲1deg之測定條件測定。將最低之黏度值(η)定為最低熔融黏度。 For the resin composition layers of the adhesive films produced in the examples and the comparative examples, a melt viscosity was measured using a dynamic viscoelasticity measuring apparatus ("Rheosol-G3000" manufactured by UBM). With respect to 1.8 g of the sample resin composition, a parallel plate having a diameter of 18 mm was used, and the temperature was raised from a measurement start temperature of 60° C. at a temperature increase rate of 5° C./min, and measured at a measurement temperature of 2.5° C., a vibration number of 1 Hz, and a distortion of 1 deg. The lowest viscosity value (η) is defined as the lowest melt viscosity.

<實施例1> <Example 1> (1)樹脂清漆之調製 (1) Modification of resin varnish

將雙酚型環氧樹脂(新日鐵住金化學(股)製「ZX1059」、雙酚A型與雙酚F型之1：1混合品、環氧當量約169)3份、2官能脂肪族環氧樹脂(三菱化學(股)製「YL7410」、環氧當量418)2份、聯苯型環氧樹脂(日本化藥(股)製「NC3000L」、環氧當量約269)4.5份、聯二甲苯醇型環氧樹脂(三菱化學(股)製 「YX4000HK」、環氧當量約185)3份邊於溶劑油10份攪拌邊使其加熱溶解。冷卻至室溫後，溶解磷酸酯型陰離子界面活性劑(東邦化學工業(股)製「RS-610」)1份，添加平均粒徑1.1μm之氮化鋁((股)德山製「Shapal H」、比表面積2.5m2/g、比重3.0g/cm3，以下稱為「氮化鋁1」)34份、平均粒徑4.7μm之氮化鋁((股)德山製「Shapal H」、比表面積1.0m2/g、比重3.1g/cm3，以下稱為「氮化鋁2」)34份、平均粒徑22.3μm之氮化鋁((股)德山製「Shapal H」、比表面積0.2m2/g、比重2.9g/cm3，以下稱為「氮化鋁3」)136份，以三輥混練使其分散。對其混合苯氧基樹脂(三菱化學(股)製「YL7553」、固形分30質量%之甲基乙基酮(MEK)與環己酮之1：1溶液)5.5份、液狀酚系硬化劑(至少具有烯丙基及烷基之液狀酚)群榮化學工業(股)製「ACG-1」、羥基當量約230、重量平均分子量1690)5.5份、硬化促進劑(4-二甲基胺基吡啶(DMAP)、固形分5質量%之MEK溶液)4.5份，調製樹脂清漆。 Bisphenol type epoxy resin (ZX1059) made by Nippon Steel & Sumitomo Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent of about 169) 3 parts, 2 functional aliphatic 2 parts of epoxy resin ("Yellow"("7410", epoxide equivalent 418), biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 269), 4.5 parts, 3 parts of a xylene alcohol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Co., Ltd., and an epoxy equivalent of about 185) was dissolved while stirring with 10 parts of a solvent oil. After cooling to room temperature, 1 part of a phosphate ester type anionic surfactant ("RS-610" manufactured by Toho Chemical Co., Ltd.) was dissolved, and aluminum nitride having an average particle diameter of 1.1 μm ("Shapal" manufactured by Tokuyama) was added. H", a specific surface area of 2.5 m 2 /g, a specific gravity of 3.0 g/cm 3 , hereinafter referred to as "aluminum nitride 1"), 34 parts of aluminum nitride having an average particle diameter of 4.7 μm ("Shadal H""Aluminum nitride having a specific surface area of 1.0 m 2 /g, a specific gravity of 3.1 g/cm 3 , hereinafter referred to as "aluminum nitride 2"), and an average particle diameter of 22.3 μm ("Shapal H" manufactured by Tokuyama 136 parts of a specific surface area of 0.2 m 2 /g and a specific gravity of 2.9 g/cm 3 (hereinafter referred to as "aluminum nitride 3") were dispersed by three rolls. Mixed with phenoxy resin ("7555" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of methyl ethyl ketone (MEK) and cyclohexanone in a solid content of 30% by mass), liquid phenolic hardening (a liquid phenol having at least an allyl group and an alkyl group) "ACG-1" manufactured by Kyoei Chemical Industry Co., Ltd., a hydroxyl equivalent of about 230, a weight average molecular weight of 1690), 5.5 parts, and a hardening accelerator (4-dimethyl) A resin varnish was prepared by subjecting a base amide (DMAP) and a solid content of 5% by mass of MEK solution to 4.5 parts.

(2)接著薄膜之製作 (2) Following the production of the film

準備附脫膜層的PET薄膜(Lintec(股)製「PET501010」、厚度50μm)作為支持體。於該支持體之脫膜層側，以乾燥後之樹脂組成物層的厚度成為100μm的方式，均勻塗佈樹脂清漆，使其於75℃~120℃乾燥10分鐘，製作接著薄膜。 A PET film ("PET501010" manufactured by Lintec Co., Ltd., thickness: 50 μm) with a release layer was prepared as a support. The resin varnish was uniformly applied to the release layer side of the support so that the thickness of the dried resin composition layer was 100 μm, and the resultant was dried at 75 ° C to 120 ° C for 10 minutes to prepare a film.

<實施例2> <Example 2>

除了於三輥之混練後進一步加入碳二醯亞胺化合物(日清紡化學(股)製「V-03」、固形分51%、黏度38mPa．s(20℃))2份之外，其他與實施例1同樣進行，來製作接著薄膜。 In addition to the addition of the carbodiimide compound ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., solid content 51%, viscosity 38 mPa.s (20 °C)) after the mixing of the three rolls, the other implementation Example 1 was carried out in the same manner to produce a film.

<實施例3> <Example 3>

除了將氮化鋁1的摻合量變更為17份，將氮化鋁2的摻合量變更為51份之外，其他與實施例1同樣進行來製作接著薄膜。 An adhesive film was produced in the same manner as in Example 1 except that the blending amount of the aluminum nitride 1 was changed to 17 parts, and the blending amount of the aluminum nitride 2 was changed to 51 parts.

<實施例4> <Example 4>

除了將氮化鋁1的摻合量變更為43.5份，將氮化鋁2的摻合量變更為43.5份，將氮化鋁3之摻合量變更為116份之外，其他與實施例1同樣進行來製作接著薄膜。 The amount of the aluminum nitride 1 blended was changed to 43.5 parts, the blending amount of the aluminum nitride 2 was changed to 43.5 parts, and the blending amount of the aluminum nitride 3 was changed to 116 parts, and the same as in the first embodiment. The same process was carried out to make a film.

<實施例5> <Example 5>

除了將氮化鋁1的摻合量變更為63.8份，將氮化鋁2的摻合量變更為38.3份，將氮化鋁3之摻合量變更為102份之外，其他與實施例1同樣進行來製作接著薄膜。 In addition to changing the blending amount of aluminum nitride 1 to 63.8 parts, the blending amount of aluminum nitride 2 was changed to 38.3 parts, and the blending amount of aluminum nitride 3 was changed to 102 parts, and other examples 1 The same process was carried out to make a film.

<實施例6> <Example 6>

除了將氮化鋁1的摻合量變更為72.5份，將氮化鋁2 的摻合量變更為14.5份，將氮化鋁3之摻合量變更為116份之外，其他與實施例1同樣進行來製作接著薄膜。 In addition to changing the blending amount of aluminum nitride 1 to 72.5 parts, aluminum nitride 2 The subsequent film was produced in the same manner as in Example 1 except that the blending amount was changed to 14.5 parts and the blending amount of the aluminum nitride 3 was changed to 116 parts.

<實施例7> <Example 7>

除了將氮化鋁1的摻合量變更為38.1份，將氮化鋁2的摻合量變更為38.1份，將氮化鋁3之摻合量變更為127份之外，其他與實施例1同樣進行來製作接著薄膜。 The amount of the aluminum nitride 1 blended was changed to 38.1 parts, the blending amount of the aluminum nitride 2 was changed to 38.1 parts, and the blending amount of the aluminum nitride 3 was changed to 127 parts, and the same as in the first embodiment. The same process was carried out to make a film.

<實施例8> <Example 8>

雙酚型環氧樹脂(新日鐵住金化學(股)製「ZX1059」、雙酚A型與雙酚F型之1：1混合品、環氧當量約169)5份、聯苯型環氧樹脂(日本化藥(股)製「NC3000L」、環氧當量約269)4.5份、聯二甲苯醇型環氧樹脂(三菱化學(股)製「YX4000HK」、環氧當量約185)3份邊於溶劑油10份攪拌邊使其加熱溶解。冷卻至室溫後，溶解磷酸酯型陰離子界面活性劑(東邦化學工業(股)製「RS-710」)1份，添加平均粒徑1.5μm之氮化鋁((股)德山製「Shapal H(耐水處理品)」、比表面積2.5m2/g、比重3.3g/cm3，以下稱為「氮化鋁4」)34份、平均粒徑5.2μm之氮化鋁((股)德山製「Shapal H(耐水處理品)」、比表面積0.8m2/g、比重3.3g/cm3，以下稱為「氮化鋁5」)34份、平均粒徑23.0μm之氮化鋁((股)德山製「Shapal H(耐水處理品)」、比表面積0.2m2/g、比重3.0g/cm3，以下稱為「氮化鋁6」)136 份，以三輥混練使其分散。對其混合苯氧基樹脂(三菱化學(股)製「YL7553」、固形分30質量%之甲基乙基酮(MEK)與環己酮之1：1溶液)5.5份、液狀酚系硬化劑(群榮化學工業(股)製「ACG-1」、羥基當量約230、重量平均分子量1690)5.5份、硬化促進劑(4-二甲基胺基吡啶(DMAP)、固形分5質量%之MEK溶液)4.5份，調製樹脂清漆，與實施例1同樣進行來製作接著薄膜。 Bisphenol type epoxy resin (ZX1059 made by Nippon Steel & Sumitomo Chemical Co., Ltd.), 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent of about 169) 5 parts, biphenyl type epoxy Resin (Nippon Chemical Co., Ltd. "NC3000L", epoxy equivalent of about 269) 4.5 parts, xylene glycol epoxy resin ("XX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185) The solvent oil was heated and dissolved by stirring 10 parts. After cooling to room temperature, 1 part of a phosphate ester type anionic surfactant ("RS-710" manufactured by Toho Chemical Co., Ltd.) was dissolved, and aluminum nitride having an average particle diameter of 1.5 μm was added (Shapal, manufactured by Tokuyama) H (water-resistant)", specific surface area: 2.5 m 2 /g, specific gravity: 3.3 g/cm 3 , hereinafter referred to as "aluminum nitride 4"), 34 parts, and aluminum nitride having an average particle diameter of 5.2 μm Yamato "Shapal H (water-resistant product)", specific surface area 0.8 m 2 /g, specific gravity 3.3 g/cm 3 , hereinafter referred to as "aluminum nitride 5") 34 parts, aluminum nitride having an average particle diameter of 23.0 μm ( (shares) 136 parts of "Shapal H (water-resistant product)", "Special Surface Area 0.2m 2 /g, Specific Gravity 3.0g/cm 3 , hereinafter referred to as "Aluminum Nitride 6"), and three-roller kneading dispersion. Mixed with phenoxy resin ("7555" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of methyl ethyl ketone (MEK) and cyclohexanone in a solid content of 30% by mass), liquid phenolic hardening Agent (ACG-1), group AC Chemical Co., Ltd., hydroxyl equivalent: about 230, weight average molecular weight 1690), 5.5 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content: 5% by mass) 4.5 parts of the MEK solution), and a resin varnish was prepared, and the following film was produced in the same manner as in Example 1.

<實施例9> <Example 9>

除了將液狀酚系硬化劑變更為明和化成(股)製「MEH-8000H」(具有烯丙基之液狀酚、羥基當量約140)5.5份之外，其他與實施例8同樣進行來製作接著薄膜。 The same procedure as in Example 8 was carried out, except that the liquid phenolic curing agent was changed to "MEH-8000H" (liquid phenol having an allyl group and a hydroxyl group equivalent of about 140) manufactured by Minghe Chemical Co., Ltd., 5.5 parts. Then the film.

<實施例10> <Example 10>

除了將氮化鋁4的摻合量變更為17.0份，將氮化鋁5之摻合量變更為51.0份，將硬化促進劑變更為四丁基鏻癸酸鹽(TBPDA)(固形分10質量%之MEK溶液)6份之外，其他與實施例8同樣進行來製作接著薄膜。 In addition to changing the blending amount of aluminum nitride 4 to 17.0 parts, the blending amount of aluminum nitride 5 was changed to 51.0 parts, and the hardening accelerator was changed to tetrabutyl niobate (TBPDA) (solid content 10 mass) A subsequent film was produced in the same manner as in Example 8 except that 6 parts of the MEK solution was used.

<實施例11> <Example 11>

除了將氮化鋁4的摻合量變更為37.8份，將氮化鋁5之摻合量變更為37.8份，取代氮化鋁6，改添加平均粒徑 30μm之氮化鋁((股)德山製「Shapal H(耐水處理品)」、比表面積0.2m2/g、比重3.3g/cm3，以下稱為「氮化鋁7」)126份，將苯氧基樹脂變更為「YL7482」(三菱化學(股)製、固形分30質量%之甲基乙基酮(MEK)與環己酮之1：1溶液)5.5份之外，其他與實施例10同樣進行來製作接著薄膜。 In addition to changing the blending amount of aluminum nitride 4 to 37.8 parts, the blending amount of aluminum nitride 5 was changed to 37.8 parts, and instead of aluminum nitride 6, aluminum nitride having an average particle diameter of 30 μm was added. Hill Ltd. "Shapal H (water-treated product)", a specific surface area 0.2m 2 / g, specific gravity of 3.3g / cm 3, hereinafter referred to as "aluminum nitride 7"), 126 parts of phenoxy resin will change to "YL7482" A film of the following was produced in the same manner as in Example 10 except that 5.5 parts of methyl ethyl ketone (MEK) and cyclohexanone (1:1) in a solid content of 30% by mass (manufactured by Mitsubishi Chemical Co., Ltd.) was used.

<實施例12> <Example 12>

除了將磷酸酯型陰離子界面活性劑之摻合量變更為1.2份，將氮化鋁4的摻合量變更為44.4份，取代氮化鋁5改添加平均粒徑4μm之氧化鋁(昭和電工(股)製「CB-P05」、比表面積0.7m2/g、比重2.2g/cm3，以下稱為「氧化鋁2」)44.4份，取代氮化鋁6改添加平均粒徑28μm之氧化鋁(昭和電工(股)製「CB-A30S」、比表面積0.2m2/g、比重2.3g/cm3，以下稱為「氧化鋁3」)148份，將苯氧基樹脂變更為「YL7482」之外，其他與實施例8同樣進行來製作接著薄膜。 In addition to changing the blending amount of the phosphate ester type anionic surfactant to 1.2 parts, the blending amount of aluminum nitride 4 was changed to 44.4 parts, and aluminum oxide was replaced by aluminum nitride 5 instead of alumina having an average particle diameter of 4 μm (Showa Electric ( "CB-P05", a specific surface area of 0.7 m 2 /g, a specific gravity of 2.2 g/cm 3 , hereinafter referred to as "alumina 2"), 44.4 parts, instead of aluminum nitride 6, an alumina having an average particle diameter of 28 μm was added. (Showing Electric Co., Ltd., "CB-A30S", specific surface area: 0.2 m 2 /g, specific gravity: 2.3 g/cm 3 , hereinafter referred to as "alumina 3") 148 parts, and changing phenoxy resin to "YL7482" The film was produced in the same manner as in Example 8 except that the film was formed in the same manner as in Example 8.

<實施例13> <Example 13>

除了將磷酸酯型陰離子界面活性劑之摻合量變更為1.1份，取代氮化鋁4改添加平均粒徑1μm之氧化鋁(日本輕金屬(股)製「AHP300」、比表面積2.6m2/g、比重3.98g/cm3，以下稱為「氧化鋁1」)40.8份，將氧化鋁2的摻合量變更為40.8份，取代氧化鋁3改添加136份之 氮化鋁7，將硬化促進劑變更為四丁基鏻癸酸鹽(TBPDA)(固形分10質量%之MEK溶液)6份之外，其他與實施例12同樣進行來製作接著薄膜。 In addition to changing the blending amount of the phosphate-type anionic surfactant to 1.1 parts, aluminum oxide (AHP300, manufactured by Nippon Light Metal Co., Ltd.) having a specific particle diameter of 2.6 m 2 /g was added instead of aluminum nitride 4 . 40.8 parts of a specific gravity of 3.98 g/cm 3 (hereinafter referred to as "alumina 1"), 40.8 parts of the amount of alumina 2 blended, and 136 parts of aluminum nitride 7 instead of alumina 3, and hardening promotion A film was formed in the same manner as in Example 12 except that the amount of the agent was changed to 6 parts of tetrabutyl phthalate (TBPDA) (solid content: 10% by mass of MEK solution).

<實施例14> <Example 14>

除了將硬化促進劑變更為4-二甲基胺基吡啶(DMAP)、固形分5質量%之MEK溶液)4.5份之外，其他與實施例13同樣進行來製作接著薄膜。 An adhesive film was produced in the same manner as in Example 13 except that the hardening accelerator was changed to 4.5 parts of 4-dimethylaminopyridine (DMAP) and a solid content of 5% by mass of MEK solution.

<比較例1> <Comparative Example 1>

除了i)將氮化鋁1的摻合量變更為17份，將氮化鋁2的摻合量變更為51份的點、ii)取代液狀酚系硬化劑(群榮化學工業(股)製「ACG-1」、活性基當量約230)5.5份，改使用固體狀酚系硬化劑(DIC(股)製「LA7054」、含有三嗪結構之酚酚醛清漆樹脂、活性基當量約125、固形分60質量%之MEK溶液)5份及固體狀萘酚系硬化劑(新日鐵住金化學(股)製「SN-485」、羥基當量215、固形分50%之MEK溶液)5份的點之外，其他與實施例1同樣進行來製作接著薄膜。 In addition to i) changing the blending amount of aluminum nitride 1 to 17 parts, changing the blending amount of aluminum nitride 2 to 51 parts, and ii) replacing the liquid phenol-based hardener (Group Rong Chemical Industry Co., Ltd.) 5.5 parts of "ACG-1" and an active base equivalent of about 230), and a solid phenolic curing agent ("LA7054" manufactured by DIC Co., Ltd., a phenol novolak resin containing a triazine structure, and an active group equivalent of about 125," 5 parts of solid solution (60% by mass of MEK solution) and solid naphthol-based curing agent ("SN-485" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., hydroxyl equivalent 215, 50% solid MEK solution)) Other than the point, the film was produced in the same manner as in Example 1.

<比較例2> <Comparative Example 2>

除了i)未使用氮化鋁1的點、ii)將氮化鋁2的摻合量變更為68份的點之外，其他與實施例1同樣進行來製作接著薄膜。 A subsequent film was produced in the same manner as in Example 1 except that i) where no aluminum nitride 1 was used, and ii) a blending amount of aluminum nitride 2 was changed to 68 parts.

<比較例3> <Comparative Example 3>

除了i)將氮化鋁1的摻合量變更為68份的點、ii)未使用氮化鋁2的點之外，其他與實施例1同樣進行來製作接著薄膜。 A subsequent film was produced in the same manner as in Example 1 except that i) the amount of the aluminum nitride 1 blended was changed to 68 parts, and ii) the point where the aluminum nitride 2 was not used.

<比較例4> <Comparative Example 4>

除了i)將氮化鋁1的摻合量變更為51份，將氮化鋁2的摻合量變更為153份的點、ii)未使用氮化鋁3的點之外，其他與實施例1同樣進行來製作接著薄膜。 Except for i) changing the blending amount of aluminum nitride 1 to 51 parts, changing the blending amount of aluminum nitride 2 to 153 parts, ii) not using aluminum nitride 3, and other examples 1 was carried out in the same manner to produce a film.

將結果示於表1、表2。惟，針對比較例1、2及4，由於熔融黏度高且熱傳導率測定用之硬化物試料的製作困難，故未記載熱傳導率之值。又，針對比較例2及4，由於熔融黏度高且測定．評估用基板之製作困難，故未記載密著強度之值。 The results are shown in Tables 1 and 2. However, in Comparative Examples 1, 2, and 4, since the melt viscosity was high and the cured sample for thermal conductivity measurement was difficult to produce, the value of the thermal conductivity was not described. Further, for Comparative Examples 2 and 4, the melt viscosity was high and measured. Since the production of the evaluation substrate is difficult, the value of the adhesion strength is not described.

Claims (24)

一種樹脂組成物，其係包含(A)環氧樹脂、(B)硬化劑及(C)無機填充材之樹脂組成物，(B)成分係包含液狀酚系硬化劑，(C)成分係包含(C1)平均粒徑0.1μm以上未滿3μm之無機填充材、(C2)平均粒徑3μm以上未滿10μm之無機填充材及(C3)平均粒徑10μm以上且35μm以下之無機填充材。 A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) a resin composition of an inorganic filler, (B) a component comprising a liquid phenolic curing agent, and (C) a component (C1) an inorganic filler having an average particle diameter of 0.1 μm or more and less than 3 μm, (C2) an inorganic filler having an average particle diameter of 3 μm or more and less than 10 μm, and (C3) an inorganic filler having an average particle diameter of 10 μm or more and 35 μm or less. 如請求項1之樹脂組成物，其中，將(C)成分的含量定為100質量%的情況下，(C1)成分的含量為5質量%~40質量%、(C2)成分的含量為5質量%~40質量%、(C3)成分的含量為20質量%~90質量%。 In the resin composition of claim 1, wherein the content of the component (C) is 100% by mass, the content of the component (C1) is 5% by mass to 40% by mass, and the content of the component (C2) is 5. The content of the mass % to 40% by mass and the (C3) component is 20% by mass to 90% by mass. 如請求項1之樹脂組成物，其中，將(C1)成分之平均粒徑定為dc1(μm)，將(C2)成分之平均粒徑定為dc2(μm)，將(C3)成分之平均粒徑定為dc3(μm)時，dc1、dc2及dc3係滿足dc2-dc1≧0.5及dc3-dc2≧5.0的關係。 The resin composition of claim 1, wherein the average particle diameter of the component (C1) is d c1 (μm), and the average particle diameter of the component (C2) is d c2 (μm), and the component (C3) is obtained. When the average particle diameter is set to d c3 (μm), d c1 , d c2 and d c3 satisfy the relationship of d c2 - d c1 ≧ 0.5 and d c3 - d c2 ≧ 5.0. 如請求項1之樹脂組成物，其中，將樹脂組成物中之不揮發成分定為100體積%的情況下，(C)成分的含量為60體積%~90體積%。 In the resin composition of claim 1, wherein the non-volatile content in the resin composition is 100% by volume, the content of the component (C) is 60% by volume to 90% by volume. 如請求項1之樹脂組成物，其中，(C)成分係包含熱傳導率25W/m．K以上之無機填充材。 The resin composition of claim 1, wherein the component (C) comprises a thermal conductivity of 25 W/m. An inorganic filler of K or more. 如請求項1之樹脂組成物，其中，(C)成分係包含選自由氮化鋁、氧化鋁、氮化硼、氮化矽及碳化矽所構 成之群組中之1或2以上的無機填充材。 The resin composition of claim 1, wherein the component (C) comprises a material selected from the group consisting of aluminum nitride, aluminum oxide, boron nitride, tantalum nitride, and tantalum carbide. One or more inorganic fillers in the group. 如請求項1之樹脂組成物，其中，(C)成分係包含氮化鋁。 The resin composition of claim 1, wherein the component (C) comprises aluminum nitride. 如請求項1之樹脂組成物，其中，(A)成分係包含液狀環氧樹脂。 The resin composition of claim 1, wherein the component (A) comprises a liquid epoxy resin. 如請求項1之樹脂組成物，其係進一步包含(D)硬化促進劑。 The resin composition of claim 1, which further comprises (D) a hardening accelerator. 如請求項9之樹脂組成物，其中，(D)成分係包含四取代鏻鹽。 The resin composition of claim 9, wherein the component (D) comprises a tetra-substituted phosphonium salt. 如請求項1之樹脂組成物，其係進一步包含(E)碳二醯亞胺化合物。 The resin composition of claim 1, which further comprises (E) a carbodiimide compound. 一種接著薄膜，其係包含支持體、與樹脂組成物層，該樹脂組成物層係由與該支持體接合之如請求項1~11中任一項之樹脂組成物所構成。 An adhesive film comprising a support and a resin composition layer, the resin composition layer being composed of the resin composition according to any one of claims 1 to 11 bonded to the support. 如請求項12之接著薄膜，其中，樹脂組成物層之最低熔融黏度為500泊~20000泊。 The film of claim 12, wherein the resin composition layer has a minimum melt viscosity of from 500 poise to 20,000 poise. 如請求項12之接著薄膜，其中，將(C3)成分之平均粒徑定為dc3(μm)時，樹脂組成物層之厚度為(dc3+45)μm~200μm。 The requested item 12 when the next film, wherein the average particle diameter of the component (C3) as d c3 (μm), the thickness of the resin composition layer of (d c3 +45) μm ~ 200μm . 如請求項12之接著薄膜，其係高熱傳導用。 The film, as claimed in item 12, is for high heat conduction. 如請求項12之接著薄膜，其係使用在金屬放熱體與半導體模組的接著。 The film, as claimed in claim 12, is used in conjunction with the metal heat sink and the semiconductor module. 一種印刷配線板，其係包含藉由如請求項1~11中任一項之樹脂組成物的硬化物所形成之絕緣層。 A printed wiring board comprising an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 11. 一種功率半導體裝置，其係包含具有第1及第2主面之金屬放熱體、具有第1及第2主面之半導體模組、及絕緣層，該絕緣層係以金屬放熱體之第1主面與半導體模組之第2主面進行接合的方式，藉由設置於金屬放熱體與半導體模組之間的如請求項1~11中任一項之樹脂組成物的硬化物而形成。 A power semiconductor device comprising a metal heat sink having first and second main faces, a semiconductor module having first and second main faces, and an insulating layer, wherein the insulating layer is a first main body of the metal heat radiator The surface is bonded to the second main surface of the semiconductor module, and is formed by a cured product of the resin composition according to any one of claims 1 to 11 between the metal heat sink and the semiconductor module. 如請求項18之功率半導體裝置，其中，金屬放熱體之第1主面及半導體模組之第2主面之至少一者的算術平均粗糙度(Ra)為500nm以下。 The power semiconductor device according to claim 18, wherein the arithmetic mean roughness (Ra) of at least one of the first main surface of the metal heat radiator and the second main surface of the semiconductor module is 500 nm or less. 如請求項18之功率半導體裝置，其中，絕緣層之熱傳導率為8W/m．K以上，絕緣層與金屬放熱體之第1主面及半導體模組之第2主面之至少一者的密著強度為0.5kgf/cm以上。 The power semiconductor device of claim 18, wherein the thermal conductivity of the insulating layer is 8 W/m. K or more, the adhesion strength between the insulating layer and at least one of the first main surface of the metal heat radiator and the second main surface of the semiconductor module is 0.5 kgf/cm or more. 一種層合體，其係絕緣層與金屬層之層合體，絕緣層之熱傳導率為8W/m．K以上，且絕緣層與金屬層的密著強度為0.5kgf/cm以上。 A laminate, which is a laminate of an insulating layer and a metal layer, and the thermal conductivity of the insulating layer is 8 W/m. K or more, and the adhesion strength between the insulating layer and the metal layer is 0.5 kgf/cm or more. 如請求項21之層合體，其中，與金屬層之絕緣層接合之表面的算術平均粗糙度(Ra)為500nm以下。 The laminate of claim 21, wherein the surface to be bonded to the insulating layer of the metal layer has an arithmetic mean roughness (Ra) of 500 nm or less. 如請求項21之層合體，其中，金屬層係由銅或鋁所構成。 A laminate according to claim 21, wherein the metal layer is composed of copper or aluminum. 如請求項21之層合體，其中，絕緣層係藉由如請求項1~11中任一項之樹脂組成物的硬化物形成而成。 The laminate of claim 21, wherein the insulating layer is formed by a cured product of the resin composition according to any one of claims 1 to 11.
TW105103846A 2015-02-05 2016-02-04 Resin composition TWI696657B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-021416 2015-02-05
JP2015021416 2015-02-05

Publications (2)

Publication Number Publication Date
TW201704333A true TW201704333A (en) 2017-02-01
TWI696657B TWI696657B (en) 2020-06-21

Family

ID=56564012

Family Applications (1)

Application Number Title Priority Date Filing Date
TW105103846A TWI696657B (en) 2015-02-05 2016-02-04 Resin composition

Country Status (3)

Country Link
JP (1) JP6772841B2 (en)
TW (1) TWI696657B (en)
WO (1) WO2016125664A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI663203B (en) * 2017-02-14 2019-06-21 日商京瓷股份有限公司 Resin sheet, semiconductor device, and method for manufacturing semiconductor device
CN110577722A (en) * 2019-09-12 2019-12-17 江苏硕阳电子科技有限公司 Epoxy resin mixed heat-conducting insulating material for air-core reactor and preparation method thereof
CN111247207A (en) * 2017-10-18 2020-06-05 三键有限公司 Thermally conductive resin composition, cured product, and heat dissipation method
CN114591708A (en) * 2020-12-30 2022-06-07 广东生益科技股份有限公司 Resin composition, resin adhesive film and application thereof

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6696380B2 (en) * 2016-09-20 2020-05-20 トヨタ自動車株式会社 Semiconductor device
JP7102093B2 (en) * 2016-09-28 2022-07-19 味の素株式会社 Resin composition, resin sheet, circuit board and semiconductor chip package
JP6787210B2 (en) * 2017-03-23 2020-11-18 味の素株式会社 Resin composition
WO2019106953A1 (en) * 2017-11-30 2019-06-06 京セラ株式会社 Resin sheet, semiconductor device and method for producing semiconductor device
JP7099009B2 (en) * 2018-03-30 2022-07-12 住友ベークライト株式会社 Heat dissipation insulation sheet and semiconductor device
WO2020067364A1 (en) * 2018-09-28 2020-04-02 富士フイルム株式会社 Composition for forming heat conductive materials, heat conductive material, heat conductive sheet, device with heat conductive layer, and film
CN112041411B (en) * 2018-12-25 2022-04-01 富士高分子工业株式会社 Thermally conductive composition and thermally conductive sheet using same
US11781053B2 (en) 2018-12-25 2023-10-10 Fuji Polymer Industries Co., Ltd. Thermally conductive composition and thermally conductive sheet using the same
WO2020188641A1 (en) * 2019-03-15 2020-09-24 日立化成株式会社 Epoxy resin composition, electronic component device, and method for manufacturing electronic component device
JPWO2022113941A1 (en) * 2020-11-30 2022-06-02
WO2023181905A1 (en) * 2022-03-22 2023-09-28 日本発條株式会社 Laminate manufacturing method

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006176549A (en) * 2004-12-20 2006-07-06 Sumitomo Bakelite Co Ltd Epoxy resin composition and semiconductor device
JP5270833B2 (en) * 2006-12-20 2013-08-21 パナソニック株式会社 Liquid resin composition, semiconductor device and manufacturing method thereof
JP5273745B2 (en) * 2010-09-10 2013-08-28 信越化学工業株式会社 Overcoat material and semiconductor device using the same
JP5622267B2 (en) * 2010-09-30 2014-11-12 新日鉄住金化学株式会社 Adhesive resin composition, cured product thereof, and adhesive film
JP5767916B2 (en) * 2011-09-06 2015-08-26 日清紡ホールディングス株式会社 Electrically insulating resin composition and metal substrate
JP6123277B2 (en) * 2011-12-28 2017-05-10 日立化成株式会社 RESIN COMPOSITION, RESIN COMPOSITION SHEET, AND METHOD FOR PRODUCING RESIN COMPOSITION SHEET, RESIN COMPOSITION SHEET WITH METAL FILMS, B STAGE SHEET, RESIN COMPOSITION SHEET WITH SEMI-HARDENED METAL FILMS, METAL BASE WIRING BOARD MATERIAL, METAL BASE WIRING BOARD , LED light source member, and power semiconductor device
JP2013189625A (en) * 2012-02-15 2013-09-26 Nippon Steel & Sumikin Chemical Co Ltd High thermal conductive resin cured product, high thermal conductive semicured resin film, and high thermal conductive resin composition
JP2015130476A (en) * 2013-12-04 2015-07-16 日東電工株式会社 Epoxy resin composition for optical semiconductor device and lead frame for optical semiconductor device obtained by using the same, sealed optical semiconductor element and optical semiconductor device

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI663203B (en) * 2017-02-14 2019-06-21 日商京瓷股份有限公司 Resin sheet, semiconductor device, and method for manufacturing semiconductor device
CN111247207A (en) * 2017-10-18 2020-06-05 三键有限公司 Thermally conductive resin composition, cured product, and heat dissipation method
CN111247207B (en) * 2017-10-18 2022-11-08 三键有限公司 Thermally conductive resin composition, cured product, and heat dissipation method
CN110577722A (en) * 2019-09-12 2019-12-17 江苏硕阳电子科技有限公司 Epoxy resin mixed heat-conducting insulating material for air-core reactor and preparation method thereof
CN114591708A (en) * 2020-12-30 2022-06-07 广东生益科技股份有限公司 Resin composition, resin adhesive film and application thereof
WO2022141816A1 (en) * 2020-12-30 2022-07-07 广东生益科技股份有限公司 Resin composition, resin adhesive film, and application thereof
CN114591708B (en) * 2020-12-30 2023-04-07 广东生益科技股份有限公司 Resin composition, resin adhesive film and application thereof

Also Published As

Publication number Publication date
JP6772841B2 (en) 2020-10-21
WO2016125664A1 (en) 2016-08-11
JPWO2016125664A1 (en) 2017-11-16
TWI696657B (en) 2020-06-21

Similar Documents

Publication Publication Date Title
TWI696657B (en) Resin composition
JP7279732B2 (en) Resin composition, adhesive film, printed wiring board and semiconductor device
TWI784927B (en) resin composition
KR102577869B1 (en) Resin composition
JP6672630B2 (en) Resin composition
CN106256862B (en) Resin composition
KR102577867B1 (en) Resin composision
JP6950732B2 (en) Resin composition
TWI752246B (en) resin composition
JP7480808B2 (en) Resin composition, resin sheet, printed wiring board and semiconductor device
TW201925332A (en) Resin composition
JP2017059779A (en) Method for manufacturing printed wiring board
TWI720997B (en) Resin composition
TWI707611B (en) Resin sheet with supporting body and manufacturing method of built-in circuit board of parts using it
CN110016203B (en) Resin composition
CN109423015B (en) Resin composition
TWI793906B (en) circuit board
TWI773796B (en) resin composition
JP6940926B2 (en) Resin composition
JP6648433B2 (en) Resin composition
JP6881552B2 (en) Resin composition
JP2021091912A (en) Resin composition