TW201434948A - Curable resin composition - Google Patents

Curable resin composition Download PDF

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TW201434948A
TW201434948A TW103101277A TW103101277A TW201434948A TW 201434948 A TW201434948 A TW 201434948A TW 103101277 A TW103101277 A TW 103101277A TW 103101277 A TW103101277 A TW 103101277A TW 201434948 A TW201434948 A TW 201434948A
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resin composition
curable resin
resin
mass
epoxy resin
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TWI619761B (en
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Shigeo Nakamura
Kenji Kawai
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Ajinomoto Kk
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4028—Isocyanates; Thioisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K3/36—Silica
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

The purpose of the present invention is to provide a curable resin composition which is excellent in elongation at break, has low arithmetic mean roughness of insulation layer surface and low root mean square roughness in the wet type roughening step, can be used to form an electroplated conductor layer with sufficient tear strength and has low linear thermal expansion coefficient. The solving means of the present invention is to provide a curable resin composition which contains: (A) phenoxy resin having fluorene structure; (B) epoxy resin; and (C) curing agent and is characterized in that the curing agent (C) contains more than one selected from the group consisting of phenolic curing agent, cyanate ester curing agent, and active ester curing agent and the phenoxy resin (A) accounts for 1~20 mass% based on 100mass% of the total amount of the phenoxy resin (A), the epoxy resin (B) and the curing agent (C).

Description

硬化性樹脂組成物 Curable resin composition

本發明係關於硬化性樹脂組成物。此外，本發明係關於含有該硬化性樹脂組成物之絕緣層用硬化性樹脂組成物、薄片狀層合材料、多層印刷配線板、半導體裝置。 The present invention relates to a curable resin composition. Further, the present invention relates to a curable resin composition for an insulating layer containing the curable resin composition, a sheet-like laminate, a multilayer printed wiring board, and a semiconductor device.

近年來，電子機器的小型化、高性能化快速發展，於多層印刷配線板中，係要求增層的複數層化、配線的細微化以及高密度化。 In recent years, miniaturization and high performance of electronic devices have been rapidly progressing, and in multilayer printed wiring boards, it is required to increase the number of layers, to make the wiring finer, and to increase the density.

相對於此，係已採取各種因應做法。例如，專利文獻1係揭示一種將特定結構的高分子環氧樹脂使用作為印刷配線板用的樹脂組成物，以改善耐熱性、低吸水性、電特性、成形性、可撓性、耐衝擊性及黏著性之內容(請求項及段落號碼0003等)。然而，專利文獻1之樹脂組成物，關於其特徵為以特定比率來組合具有特定茀結構之苯氧樹脂與環氧樹脂，且包含選自酚硬化劑、氰酸酯硬化劑、活性酯硬化劑之硬化劑之硬化性樹脂組成物，並無任何記載。 In contrast, various approaches have been taken. For example, Patent Document 1 discloses that a polymer epoxy resin having a specific structure is used as a resin composition for a printed wiring board to improve heat resistance, low water absorption, electrical properties, formability, flexibility, and impact resistance. And the content of adhesion (request and paragraph number 0003, etc.). However, the resin composition of Patent Document 1 is characterized in that a phenoxy resin having a specific fluorene structure and an epoxy resin are combined at a specific ratio, and contains a phenolic hardener, a cyanate hardener, and an active ester hardener. The curable resin composition of the hardener is not described.

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

[專利文獻1]日本特開2003-252951號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-252951

本發明所欲解決之課題在於提供一種具有特定強度(破壞伸長度)，於濕式粗化步驟中不僅絕緣層表面的算術平均粗糙度低，且均方根粗糙度亦低(低粗糙度)，並且能夠形成具有充分的撕離強度之電鍍導體層，且線熱膨脹係數亦低之硬化性樹脂組成物。 The object of the present invention is to provide a specific strength (destructive elongation) in which not only the arithmetic mean roughness of the surface of the insulating layer is low but also the root mean square roughness (low roughness) in the wet roughening step. Further, it is possible to form a plated conductor layer having a sufficient tear strength and a curable resin composition having a low coefficient of thermal expansion.

本發明者們係為了解決上述課題而進行精心探討，結果發現到下列硬化性樹脂組成可達成上述優異的強度、低粗糙度、高撕離強度及低線熱膨脹係數，因而完成本發明，該硬化性樹脂組成物，係含有：(A)具有茀結構之苯氧樹脂、(B)環氧樹脂、及(C)硬化劑，其特徵為：(C)硬化劑包含選自酚硬化劑、氰酸酯硬化劑、活性酯硬化劑之1種以上，且(A)苯氧樹脂與(B)環氧樹脂與(C)硬化劑之合計為100質量%時，(A)苯氧樹脂為1~20質量%。 The present inventors have intensively studied to solve the above problems, and as a result, it has been found that the following curable resin composition can achieve the above-described excellent strength, low roughness, high tear strength, and low linear thermal expansion coefficient, and thus the present invention has been completed. The resin composition comprises: (A) a phenoxy resin having a fluorene structure, (B) an epoxy resin, and (C) a curing agent, characterized in that: (C) the hardener comprises a phenol hardener and cyanide. When the total of the (A) phenoxy resin and the (B) epoxy resin and the (C) curing agent is 100% by mass, the (A) phenoxy resin is 1 or more. ~20% by mass.

亦即，本發明係包含下列型態。 That is, the present invention encompasses the following types.

[1]一種硬化性樹脂組成物，其係含有：(A)具有茀結構之苯氧樹脂、(B)環氧樹脂、及(C)硬化劑之樹脂組成物，其特徵為：(C)硬化劑包含選自酚硬化劑、氰酸酯硬化劑、活性酯硬化劑之1種以上，且前述(A)苯氧樹脂與前述(B)環氧樹脂與前述(C)硬化劑之合計為100質量%時，前述(A)苯氧樹脂為1~20質量%。 [1] A curable resin composition comprising: (A) a phenoxy resin having a fluorene structure, (B) an epoxy resin, and (C) a resin composition of a curing agent, characterized in that: (C) The curing agent contains one or more selected from the group consisting of a phenol curing agent, a cyanate curing agent, and an active ester curing agent, and the total of the (A) phenoxy resin and the (B) epoxy resin and the (C) curing agent are When it is 100% by mass, the above (A) phenoxy resin is 1 to 20% by mass.

[2]如[1]之硬化性樹脂組成物，其中前述(A)苯氧樹脂的重量平均分子量為8000~100000。 [2] The curable resin composition according to [1], wherein the (A) phenoxy resin has a weight average molecular weight of 8,000 to 100,000.

[3]如[1]或[2]之硬化性樹脂組成物，其中前述(A)苯氧樹脂具有無取代雙酚茀結構或雙甲酚茀結構。 [3] The curable resin composition according to [1] or [2], wherein the aforementioned (A) phenoxy resin has an unsubstituted bisphenol fluorene structure or a biscresol oxime structure.

[4]如[1]至[3]中任一項之硬化性樹脂組成物，其中前述(B)環氧樹脂選自由雙酚型環氧樹脂、結晶性二官能環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂及此等環氧樹脂的混合物所組成之群組。 [4] The curable resin composition according to any one of [1] to [3] wherein the (B) epoxy resin is selected from the group consisting of a bisphenol type epoxy resin, a crystalline difunctional epoxy resin, and a dicyclopentylene A group consisting of a diene type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a mixture of such epoxy resins.

[5]如[1]至[4]中任一項之硬化性樹脂組成物，其中前述硬化性樹脂組成物中的非揮發成分為100質量%時，前述(A)苯氧樹脂的含量為0.3~10質量%，前述(B)環氧樹脂的含量為5~30質量%，前述(C)硬化劑的含量為3~20質量%。 [5] The curable resin composition according to any one of [1] to [4] wherein, when the nonvolatile component in the curable resin composition is 100% by mass, the content of the (A) phenoxy resin is 0.3 to 10% by mass, the content of the (B) epoxy resin is 5 to 30% by mass, and the content of the (C) curing agent is 3 to 20% by mass.

[6]如[1]至[5]中任一項之硬化性樹脂組成物，其中進一步含有(D)無機填料。 [6] The curable resin composition according to any one of [1] to [5] further comprising (D) an inorganic filler.

[7]如[6]之硬化性樹脂組成物，其中前述(D)無機填料的平均粒徑為0.01~5μm。 [7] The curable resin composition according to [6], wherein the (D) inorganic filler has an average particle diameter of 0.01 to 5 μm.

[8]如[6]或[7]之硬化性樹脂組成物，其中前述硬化性樹脂組成物中的非揮發成分為100質量%時之前述(D)無機填料的含量為30~90質量%。 [8] The curable resin composition according to [6] or [7], wherein the content of the (D) inorganic filler in the non-volatile component in the curable resin composition is 100% by mass to 30% by mass .

[9]如[6]至[8]中任一項之硬化性樹脂組成物，其中前述(D)無機填料為二氧化矽。 [9] The curable resin composition according to any one of [6] to [8] wherein the (D) inorganic filler is cerium oxide.

[10]一種多層印刷配線板之絕緣層用硬化性樹脂組成物，其特徵係含有如[1]至[9]中任一項之硬化性樹脂組成物。 [10] A curable resin composition for an insulating layer of a multilayer printed wiring board, which comprises the curable resin composition according to any one of [1] to [9].

[11]一種多層印刷配線板之增層用硬化性樹脂組成物，其特徵係含有如[1]至[10]中任一項之硬化性樹脂組成物。 [11] A curable resin composition for a build-up of a multilayer printed wiring board, characterized in that the curable resin composition according to any one of [1] to [10] is contained.

[12]一種薄片狀層合材料，其特徵係含有如[1]至[11]中任一項之硬化性樹脂組成物。 [12] A flaky laminate comprising the curable resin composition according to any one of [1] to [11].

[13]一種多層印刷配線板，其特徵係包含使如[1]至[11]中任一項之硬化性樹脂組成物或如[12]之薄片狀層合材料熱硬化而得到之絕緣層。 [13] A multilayer printed wiring board comprising an insulating layer obtained by thermally curing a curable resin composition according to any one of [1] to [11] or a sheet-like laminate material according to [12]. .

[14]一種多層印刷配線板，其特徵係包含使如[12]之薄片狀層合材料熱硬化而得到之絕緣層。 [14] A multilayer printed wiring board comprising an insulating layer obtained by thermally hardening a sheet-like laminate material as in [12].

[15]一種半導體裝置，其特徵係包含如[13]或[14]之多層印刷配線板。 [15] A semiconductor device characterized by comprising the multilayer printed wiring board of [13] or [14].

此外，本發明較佳係包含下列型態。 Further, the present invention preferably includes the following forms.

[A]一種硬化性樹脂組成物，其係含有：(A)具有 8000~100000的重量平均分子量，具有無取代雙酚茀結構或雙甲酚茀結構，並且具有雙二甲苯酚結構或雙酚苯乙酮結構之苯氧樹脂，(B)選自由雙酚型環氧樹脂、結晶性二官能環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂及此等環氧樹脂的混合物所組成之群組之環氧樹脂，(C)包含選自酚硬化劑、氰酸酯硬化劑、活性酯硬化劑之1種以上之硬化劑，以及(D)具有0.01~5μm的平均粒徑之二氧化矽之無機填料之樹脂組成物，其特徵為：前述(A)苯氧樹脂與前述(B)環氧樹脂與前述(C)硬化劑之合計為100質量%時，前述(A)苯氧樹脂為1~20質量%，前述硬化性樹脂組成物中的非揮發成分為100質量%時，前述(A)苯氧樹脂的含量為0.3~10質量%，前述(B)環氧樹脂的含量為5~30質量%，前述(C)硬化劑的含量為3~20質量%，以及前述(D)無機填料的含量為30~90質量%。 [A] A curable resin composition containing: (A) having 8000-100000 weight average molecular weight, having an unsubstituted bisphenol fluorene structure or a biscresol oxime structure, and having a bis xylenol structure or a bisphenol acetophenone structure phenoxy resin, (B) selected from a bisphenol ring Epoxy resin of a group consisting of an oxygen resin, a crystalline difunctional epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a mixture of such epoxy resins (C) a resin comprising one or more kinds of hardeners selected from the group consisting of a phenol curing agent, a cyanate curing agent, and an active ester curing agent, and (D) an inorganic filler having an average particle diameter of 0.01 to 5 μm. In the composition, when the total amount of the (A) phenoxy resin and the (B) epoxy resin and the (C) curing agent is 100% by mass, the (A) phenoxy resin is 1 to 20% by mass. When the non-volatile component in the curable resin composition is 100% by mass, the content of the (A) phenoxy resin is 0.3 to 10% by mass, and the content of the (B) epoxy resin is 5 to 30% by mass. The content of the (C) hardener is 3 to 20% by mass, and the content of the (D) inorganic filler is 30 to 90% by mass.

使本發明之硬化性樹脂組成物熱硬化所製作之多層印刷配線板的絕緣層，具有優異的強度(破壞伸長度)，於濕式粗化步驟中不僅絕緣層表面的算術平均粗糙度低，且均方根粗糙度亦低，並且能夠形成具有充分的撕 離強度之電鍍導體層，且線熱膨脹係數亦低。 The insulating layer of the multilayer printed wiring board produced by thermally curing the curable resin composition of the present invention has excellent strength (destructive elongation), and in the wet roughening step, not only the arithmetic mean roughness of the surface of the insulating layer is low, And the root mean square roughness is also low, and can form a full tear The electroplated conductor layer is separated from the strength, and the coefficient of linear thermal expansion is also low.

尤其在本發明中，藉由使用成分(A)之具有茀結構之苯氧樹脂，可達成上述低粗糙度及高撕離強度。此外，通常含有相對較多的無機填料之環氧樹脂組成物，其薄膜中的樹脂流動差，有時於層合之導體間產生縫隙，且進而容易使撕離強度降低，但如本發明般藉由使用成分(A)，可提升撕離強度。 In particular, in the present invention, the above-mentioned low roughness and high tear strength can be attained by using the phenoxy resin having a bismuth structure of the component (A). Further, an epoxy resin composition which usually contains a relatively large amount of an inorganic filler has a poor resin flow in a film, and sometimes a gap is formed between the laminated conductors, and further, the tear strength is easily lowered, but as in the present invention By using the component (A), the tear strength can be improved.

[硬化性樹脂組成物] [Curable resin composition]

本發明的型態之一之硬化性樹脂組成物，為一種硬化性樹脂組成物，其係含有：(A)具有茀結構之苯氧樹脂、(B)環氧樹脂、及(C)硬化劑之樹脂組成物，其特徵為：(C)硬化劑包含選自酚硬化劑、氰酸酯硬化劑、活性酯硬化劑之1種以上，且前述(A)苯氧樹脂與前述(B)環氧樹脂與前述(C)硬化劑之合計為100質量%時，前述(A)苯氧樹脂為1~20質量%。以下詳細說明本發明之硬化性樹脂組成物。 The curable resin composition according to one aspect of the present invention is a curable resin composition comprising: (A) a phenoxy resin having a fluorene structure, (B) an epoxy resin, and (C) a hardener. The resin composition is characterized in that: (C) the curing agent contains one or more selected from the group consisting of a phenol curing agent, a cyanate curing agent, and an active ester curing agent, and the (A) phenoxy resin and the aforementioned (B) ring When the total of the oxygen resin and the hardener (C) is 100% by mass, the (A) phenoxy resin is 1 to 20% by mass. The curable resin composition of the present invention will be described in detail below.

(A)具有茀結構之苯氧樹脂 (A) phenoxy resin having a bismuth structure

本發明所能夠使用之具有茀結構之苯氧樹脂，只要是至少具有1種以上之下列所示的茀結構之苯氧樹脂，則可使用任意的苯氧樹脂。 The phenoxy resin having a fluorene structure which can be used in the present invention may be any phenoxy resin as long as it is a phenoxy resin having at least one of the following fluorene structures.

茀結構： 茀 structure:

茀結構佳為雙酚茀結構。該苯氧樹脂，除了茀結構之外，可任意地具有至少1種以上的雙二甲苯酚結構及雙酚苯乙酮結構。各結構可由下列式(1)~(3)表示。 The ruthenium structure is preferably a bisphenol fluorene structure. The phenoxy resin may optionally have at least one type of bisxylenol structure and bisphenol acetophenone structure in addition to the oxime structure. Each structure can be represented by the following formulas (1) to (3).

雙酚茀結構(參考日本特開2003-252951) Bisphenolphthalein structure (refer to JP-A-2003-252951)

(式(1)中，R1可互為相同或相異，為選自由氫原子、C1-10的烴基及鹵素元素所組成之群組之基，R2可互為相同或相異，為選自氫原子、C1-10的烴基或鹵素元素之基，n可互為相同或相異，為0~4的整數) (In the formula (1), R 1 may be the same or different from each other, and is a group selected from the group consisting of a hydrogen atom, a hydrocarbon group of C 1-10 and a halogen element, and R 2 may be the same or different from each other, Is a group selected from a hydrogen atom, a C 1-10 hydrocarbon group or a halogen element, and n may be the same or different from each other and is an integer of 0 to 4)

雙酚茀結構，特佳為下列結構。 The bisphenol fluorene structure is particularly preferably the following structure.

無取代雙酚茀結構 Unsubstituted bisphenol fluorene structure

雙甲酚茀結構 Dicresol structure

雙二甲苯酚結構 Dixylenol structure

雙酚苯乙酮結構(參考日本特開2003-252951) Bisphenol acetophenone structure (refer to JP-A-2003-252951)

(式(3)中，R3可互為相同或相異，為選自由氫原子、C1-10的烴基及鹵素元素所組成之群組之基，R4為選自由氫原子、C1-10的烴基及鹵素元素所組成之群組之基，R5為氫原子或C1-10的烴基，m為0~5的整數) (In the formula (3), R 3 may be the same or different from each other, and is a group selected from the group consisting of a hydrogen atom, a hydrocarbon group of C 1-10 and a halogen element, and R 4 is selected from a hydrogen atom, C 1 . the group consisting of halogen element and -10 hydrocarbon group, R 5 is a hydrogen atom or a C 1-10 hydrocarbon group, m is an integer of 0 to 5)

更佳的型態，係於式(1)中，R1可互為相同或相異，為氫原子或C1-8的烴基，較佳為氫原子或C1-6的烴基，更佳為氫原子或甲基，R2可互為相同或相異，為氫原子或C1-8的烴基，較佳為氫原子或C1-6的烴基，更佳為氫原子或甲基，特佳為氫原子，n可互為相同或相異，為0~3，較佳為1~2的整數。 More preferably, in the formula (1), R 1 may be the same or different from each other, and is a hydrogen atom or a C 1-8 hydrocarbon group, preferably a hydrogen atom or a C 1-6 hydrocarbon group, more preferably R 2 may be the same or different from each other, and may be a hydrogen atom or a C 1-8 hydrocarbon group, preferably a hydrogen atom or a C 1-6 hydrocarbon group, more preferably a hydrogen atom or a methyl group. Particularly preferred is a hydrogen atom, and n may be the same or different from each other, and is an integer of 0 to 3, preferably 1 to 2.

此外，式(3)中，R3可互為相同或相異，為氫原子或C1-8的烴基，較佳為氫原子或C1-6的烴基，更佳為氫原子或甲基，特佳為氫原子，R4為氫原子或C1-8的烴基，較佳為氫原子或C1-6的烴基，更佳為氫原子或甲基，特佳為氫原子，R5為氫原子或C1-8的烴基，較佳為氫原子或C1-6的烴基，更佳為氫原子或甲基，特佳為甲基，m為0~3，較佳為1~2的整數。 Further, in the formula (3), R 3 may be the same or different from each other, and is a hydrogen atom or a C 1-8 hydrocarbon group, preferably a hydrogen atom or a C 1-6 hydrocarbon group, more preferably a hydrogen atom or a methyl group. , particularly preferably a hydrogen atom, R 4 is a hydrogen atom or a C 1-8 hydrocarbon group, preferably a hydrogen atom or a C 1-6 hydrocarbon group, more preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom, R 5 The hydrogen atom or a C 1-8 hydrocarbon group is preferably a hydrogen atom or a C 1-6 hydrocarbon group, more preferably a hydrogen atom or a methyl group, particularly preferably a methyl group, and m is 0 to 3, preferably 1 to 2 An integer of 2.

具有茀結構之苯氧樹脂，較佳為具有至少1 種以上的茀結構、以及至少1種以上的茀結構以外之任意結構之苯氧樹脂。具體而言，較佳為具有雙二甲苯酚結構及取代或無取代的雙酚茀結構之苯氧樹脂，或是具有雙二甲苯酚結構、雙酚苯乙酮結構及雙甲酚茀結構之苯氧樹脂。更具體而言，雙酚茀結構，較佳於式(1)中，R1具有氫原子及甲基且R2為氫原子(亦即雙甲酚茀結構(1-2))。雙酚苯乙酮結構，較佳於式(3)中，R3為氫原子、R4為氫原子、R5為甲基。 The phenoxy resin having a fluorene structure is preferably a phenoxy resin having at least one or more fluorene structure and at least one or more ytterbium structures. Specifically, it is preferably a phenoxy resin having a bisxylenol structure and a substituted or unsubstituted bisphenol fluorene structure, or a bisxylenol structure, a bisphenol acetophenone structure, and a biscresol oxime structure. Phenoxy resin. More specifically, the bisphenol fluorene structure is preferably in the formula (1), and R 1 has a hydrogen atom and a methyl group and R 2 is a hydrogen atom (that is, a biscresol oxime structure (1-2)). The bisphenol acetophenone structure is preferably in the formula (3), R 3 is a hydrogen atom, R 4 is a hydrogen atom, and R 5 is a methyl group.

具有茀結構之苯氧樹脂之製造方法的一例， 可藉由使雙二甲苯酚型環氧樹脂的環氧基與雙酚茀衍生物的酚基反應而製造出。具體而言，雙二甲苯酚型環氧樹脂的環氧基數與來自雙酚茀衍生物的酚基數之比，佳為1：1~1.3：1，較佳為1：1~1.2：1，更佳為1.01：1~1.1：1。此外，為具有雙酚苯乙酮結構與雙甲酚茀結構之苯氧樹脂時，來自雙酚苯乙酮衍生物的酚基數與來自雙甲酚茀衍生物的酚基數之比，佳為1：5~1：15，較佳為1：7~1：11。藉此可降低環氧樹脂A的線熱膨脹係數。 An example of a method for producing a phenoxy resin having a fluorene structure, It can be produced by reacting an epoxy group of a bisxylenol type epoxy resin with a phenol group of a bisphenol hydrazine derivative. Specifically, the ratio of the number of epoxy groups of the bisxylenol type epoxy resin to the number of phenol groups derived from the bisphenol hydrazine derivative is preferably from 1:1 to 1.3:1, preferably from 1:1 to 1.2:1. More preferably 1.01:1~1.1:1. Further, in the case of a phenoxy resin having a bisphenol acetophenone structure and a biscresol oxime structure, the ratio of the number of phenol groups derived from the bisphenol acetophenone derivative to the number of phenol groups derived from the biscresol hydrazine derivative is preferably 1 : 5~1:15, preferably 1:7~1:11. Thereby, the linear thermal expansion coefficient of the epoxy resin A can be lowered.

具有茀結構之苯氧樹脂的含量，(A)苯氧樹 脂與後述(B)環氧樹脂與後述(C)硬化劑之合計為100質量%時，(A)苯氧樹脂為1~20質量%，佳為2~15質量%，較佳為5~12質量%。當苯氧樹脂的含量為1質量%以上時，可成為低算術平均粗糙度及低均方根粗糙度，此外，為20質量%以下時，可充分確保交聯部位，仍可成為低算術平均粗糙度及低均方根粗糙度，且可維持低線 熱膨脹係數。 The content of phenoxy resin having a bismuth structure, (A) phenoxy tree When the total amount of the fat (B) epoxy resin and the (C) hardener described later is 100% by mass, the (A) phenoxy resin is from 1 to 20% by mass, preferably from 2 to 15% by mass, preferably from 5 to 5% by mass. 12% by mass. When the content of the phenoxy resin is 1% by mass or more, the arithmetic mean roughness and the low root mean square roughness can be obtained, and when the content is 20% by mass or less, the crosslinking portion can be sufficiently ensured, and the low arithmetic mean can be obtained. Roughness and low root mean square roughness, and can maintain low line Thermal expansion coefficient.

此外，(A)苯氧樹脂與後述(B)環氧樹脂之合計為100質量%時，(A)苯氧樹脂佳為2~30質量%，較佳為4~20質量%。 Further, when the total of the (A) phenoxy resin and the epoxy resin (B) described later is 100% by mass, the (A) phenoxy resin is preferably from 2 to 30% by mass, preferably from 4 to 20% by mass.

具有茀結構之苯氧樹脂的環氧當量(含有1當量的環氧基之樹脂的質量)，佳為5000~30000(g/當量)，較佳為7000~20000(g/當量)，更佳為9000~15000(g/當量)。當具有茀結構之苯氧樹脂的環氧當量為5000以上時，具有優異的破壞伸長度，此外，為30000以下時，可充分確保交聯部位，而成為低算術平均粗糙度及低均方根粗糙度，且可維持低線熱膨脹係數。尚且，環氧當量，可依循JIS K7236(2001)來測定。 The epoxy equivalent of the phenoxy resin having a fluorene structure (the mass of the resin containing 1 equivalent of the epoxy group) is preferably 5,000 to 30,000 (g/eq), preferably 7,000 to 20,000 (g/equivalent), more preferably It is 9000~15000 (g/eq). When the epoxy equivalent of the phenoxy resin having a fluorene structure is 5,000 or more, the elongation at break is excellent, and when it is 30,000 or less, the crosslinking portion can be sufficiently ensured to have a low arithmetic mean roughness and a low root mean square. Roughness and maintain the low coefficient of thermal expansion. Further, the epoxy equivalent can be measured in accordance with JIS K7236 (2001).

具有茀結構之苯氧樹脂的重量平均分子量，例如為8000~100000，佳為15000~80000，較佳為20000~60000，更佳為25000~40000。當苯氧樹脂的重量平均分子量為8000以上時，具有優異的破壞伸長度，此外，為100000以下時，可提升與樹脂組成物之相溶性，而形成低算術平均粗糙度及低均方根粗糙度。該苯氧樹脂的重量平均分子量，可藉由凝膠滲透層析(GPC；Gel Permeation Chromatography)法來測定。具體而言，熱塑性樹脂之經聚苯乙烯換算的重量平均分子量，可使用島津製作所股份有限公司製LC-9A/RID-6A作為測定裝置，使用昭和電工股份有限公司製Shodex K-800P/K-804L/K-804L作為管柱，使用三氯甲烷作為移動相，於管柱溫度40℃進行測 定，並使用標準聚苯乙烯檢量線來算出。 The weight average molecular weight of the phenoxy resin having a fluorene structure is, for example, 8,000 to 100,000, preferably 15,000 to 80,000, preferably 20,000 to 60,000, more preferably 25,000 to 40,000. When the weight average molecular weight of the phenoxy resin is 8000 or more, the elongation at break is excellent, and when it is 100,000 or less, the compatibility with the resin composition is improved, and low arithmetic mean roughness and low root mean square roughness are formed. degree. The weight average molecular weight of the phenoxy resin can be measured by a gel permeation chromatography (GPC; Gel Permeation Chromatography) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin can be measured using LC-9A/RID-6A manufactured by Shimadzu Corporation, and Shodex K-800P/K-made by Showa Denko Co., Ltd. 804L/K-804L is used as a column, using chloroform as the mobile phase, and measuring at a column temperature of 40 °C. Determine and use a standard polystyrene calibration line to calculate.

上述硬化性樹脂組成物中的非揮發成分為100質量%時，(A)具有茀結構之苯氧樹脂的含量，佳為0.3~10質量%，較佳為0.5~7質量%，更佳為0.7~5質量%。 When the non-volatile component in the curable resin composition is 100% by mass, the content of the (A) phenoxy resin having a fluorene structure is preferably from 0.3 to 10% by mass, preferably from 0.5 to 7% by mass, more preferably 0.7 to 5 mass%.

(B)環氧樹脂 (B) Epoxy resin

(B)成分之環氧樹脂，為與(A)成分之苯氧樹脂不同之環氧樹脂。(B)成分之環氧樹脂，較佳具有與(A)成分之苯氧樹脂不同之環氧當量。(B)成分之環氧樹脂的環氧當量(含有1當量的環氧基之樹脂的質量)，佳為50~3000(g/當量)，較佳為100~2000(g/當量)，更佳為150~1000(g/當量)，特佳為200~500(g/當量)。藉此可使從硬化性樹脂組成物所得到之絕緣層的交聯密度變得充分，而有利於低粗糙度化。尚且，環氧當量，可依循JIS K7236(2001)來測定。此外，較佳者，環氧樹脂為於1分子中具有2個以上的環氧基之環氧樹脂。 The epoxy resin of the component (B) is an epoxy resin different from the phenoxy resin of the component (A). The epoxy resin of the component (B) preferably has an epoxy equivalent different from the phenoxy resin of the component (A). The epoxy equivalent of the epoxy resin of the component (B) (the mass of the resin containing 1 equivalent of the epoxy group) is preferably from 50 to 3,000 (g/equivalent), preferably from 100 to 2,000 (g/equivalent), more preferably Preferably, it is 150 to 1000 (g/equivalent), and particularly preferably 200 to 500 (g/equivalent). Thereby, the crosslinking density of the insulating layer obtained from the curable resin composition can be made sufficient, which contributes to low roughness. Further, the epoxy equivalent can be measured in accordance with JIS K7236 (2001). Further, preferably, the epoxy resin is an epoxy resin having two or more epoxy groups in one molecule.

作為具體的環氧樹脂，例如可列舉出雙酚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型環氧樹脂般之雙酚型環氧樹脂、二環戊二烯型環氧樹脂、酚-酚醛型環氧樹脂、三級丁基兒茶酚型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、萘醚型環氧樹脂、縮水甘油胺型環氧樹脂、縮水甘油酯型環氧樹脂、甲酚-酚醛型環 氧樹脂、聯苯型環氧樹脂、蒽型環氧樹脂、線狀脂肪族環氧樹脂、具有丁二烯結構之環氧樹脂、脂環型環氧樹脂、雜環型環氧樹脂、含螺旋環環氧樹脂、環己烷二甲醇環氧樹脂、三羥甲基型環氧樹脂、鹵化環氧樹脂、結晶性二官能環氧樹脂等。較佳者，(B)環氧樹脂選自由雙酚型環氧樹脂、結晶性二官能環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂及此等環氧樹脂的混合物所組成之群組。此等可使用1種或組合2種以上使用。 Specific examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and bisphenol AF epoxy resin bisphenol epoxy resin. , dicyclopentadiene type epoxy resin, phenol-phenolic epoxy resin, tertiary butyl catechol epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, naphthalene ether epoxy resin , glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type ring Oxygen resin, biphenyl type epoxy resin, bismuth type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, and spiral Ring epoxy resin, cyclohexane dimethanol epoxy resin, trimethylol epoxy resin, halogenated epoxy resin, crystalline difunctional epoxy resin, and the like. Preferably, the (B) epoxy resin is selected from the group consisting of a bisphenol type epoxy resin, a crystalline difunctional epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, and a mixture of such epoxy resins. The group formed. These may be used alone or in combination of two or more.

此等環氧樹脂中，從耐熱性提升之觀點來 看，較佳為雙酚A型環氧樹脂、雙酚F型環氧樹脂、結晶性二官能環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂及此等之2種以上的混合物。具體而言，例如可列舉出雙酚A型與F型的混合環氧樹脂(新日鐵化學股份有限公司製「ZX1059」)、雙酚A型環氧樹脂(三菱化學股份有限公司製「Epikote 828EL」、「YL980」、「jER1009」)、雙酚F型環氧樹脂(三菱化學股份有限公司製「jER806H」、「YL983U」)、萘型二官能環氧樹脂(DIC股份有限公司製「HP4032」、「HP4032D」、「HP4032SS」、「EXA4032SS」)、萘型四官能環氧樹脂(DIC股份有限公司製「HP4700」、「HP4710」)、萘酚型環氧樹脂(新日鐵化學股份有限公司製「ESN-475V」)、具有丁二烯結構之環氧樹脂(Daicel化學工業股份有限公司製「PB-3600」)、具有聯苯結構之環氧樹脂(日本化藥股份有限公司製「NC3000H」、 「NC3000L」、「NC3100」)、雙二甲苯酚型環氧樹脂(三菱化學股份有限公司製「YX4000」、「YX4000H」、「YX4000HK」、「YL6121」)、蒽型環氧樹脂(三菱化學股份有限公司製「YX8800」)、萘醚型環氧樹脂(DIC股份有限公司製「EXA7310」、「EXA7311」、「EXA7311L」、「EXA7311-G3」)、縮水甘油酯型環氧樹脂(Nagase Chemtex股份有限公司製「EX711」、「EX721」、Printec股份有限公司製「R540」)、二環戊二烯型環氧樹脂(DIC股份有限公司製「HP-7200H」)等。 Among these epoxy resins, from the viewpoint of heat resistance improvement Preferably, it is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a crystalline difunctional epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, and the like. The above mixture. Specifically, for example, a mixed epoxy resin of bisphenol A type and F type ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd.) and a bisphenol A type epoxy resin ("Epikote made by Mitsubishi Chemical Corporation") 828EL", "YL980", "jER1009"), bisphenol F type epoxy resin ("JER806H" and "YL983U" manufactured by Mitsubishi Chemical Corporation), and naphthalene type difunctional epoxy resin (HP4032, manufactured by DIC Corporation) , "HP4032D", "HP4032SS", "EXA4032SS"), naphthalene type tetrafunctional epoxy resin ("HP4700", "HP4710" manufactured by DIC Corporation), and naphthol type epoxy resin (Nippon Steel Chemical Co., Ltd.) "ESN-475V" manufactured by the company, epoxy resin having a butadiene structure ("PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.), and epoxy resin having a biphenyl structure (manufactured by Nippon Kayaku Co., Ltd.) NC3000H", "NC3000L", "NC3100"), bis(xylenol) epoxy resin ("YX4000", "YX4000H", "YX4000HK", "YL6121" manufactured by Mitsubishi Chemical Corporation), and epoxy resin (Mitsubishi Chemical Co., Ltd.) "YX8800" manufactured by the company, naphthalene ether epoxy resin (EXA7310, "EXA7311", "EXA7311L", "EXA7311-G3", manufactured by DIC Corporation), and glycidyl ester epoxy resin (Nagase Chemtex "EX711", "EX721", "R540" manufactured by Printec Co., Ltd.), dicyclopentadiene type epoxy resin ("HP-7200H" manufactured by DIC Corporation).

HP4032SS之主成分的結構式如下所述。 The structural formula of the main component of HP4032SS is as follows.

此外，YX4000HK的結構式如下所述。 In addition, the structure of the YX4000HK is as follows.

(式中，Gr為縮水甘油基) (wherein Gr is glycidyl)

此外，HP-7200H的結構式如下所述。 In addition, the structural formula of the HP-7200H is as follows.

(式中，n為1~20為止的整數) (where n is an integer from 1 to 20)

此外，NC3000L的結構式如下所述。 In addition, the structural formula of the NC3000L is as follows.

(式中，n為1~20為止的整數) (where n is an integer from 1 to 20)

此外，jER1009的結構式如下所述。 In addition, the structural formula of jER1009 is as follows.

(B)環氧樹脂的含量，(A)苯氧樹脂與前 述(B)環氧樹脂與前述(C)硬化劑之合計為100質量%時，佳為30~80質量%，較佳為35~75質量%，更佳為40~70質量%。 (B) content of epoxy resin, (A) phenoxy resin and before When the total of the (B) epoxy resin and the (C) hardener is 100% by mass, it is preferably from 30 to 80% by mass, preferably from 35 to 75% by mass, and more preferably from 40 to 70% by mass.

本發明之硬化性樹脂組成物中之(B)環氧樹脂的含量並無特別限定，從同時兼顧絕緣層的低粗糙度化與高撕離強度之觀點來看，上述硬化性樹脂組成物中的非揮發成分為100質量%時，佳為5~30質量%，較佳為7~25質量%，更佳為10~20質量%。 The content of the (B) epoxy resin in the curable resin composition of the present invention is not particularly limited, and the curable resin composition is also considered from the viewpoint of both low roughness and high tear strength of the insulating layer. When the nonvolatile content is 100% by mass, it is preferably from 5 to 30% by mass, preferably from 7 to 25% by mass, and more preferably from 10 to 20% by mass.

(C)硬化劑 (C) hardener

本申請案發明中所使用之硬化劑，係可使上述苯氧樹脂及環氧樹脂交聯而硬化，並且包含選自酚硬化劑、氰酸酯硬化劑、活性酯硬化劑之1種以上。分別構成此等酚硬化劑、氰酸酯硬化劑、活性酯硬化劑之酚樹脂、氰酸酯樹脂及活性酯樹脂，可顯著地降低絕緣層的表面粗糙度。 The curing agent used in the invention of the present invention is obtained by crosslinking and curing the phenoxy resin and the epoxy resin, and further comprising one or more selected from the group consisting of a phenol curing agent, a cyanate curing agent, and an active ester curing agent. The phenol resin, the cyanate resin, and the active ester resin constituting the phenol curing agent, the cyanate curing agent, and the active ester curing agent, respectively, can significantly reduce the surface roughness of the insulating layer.

酚樹脂並無特別限制，較佳為聯苯型酚樹 脂、萘型酚樹脂、酚-酚醛樹脂、萘醚型酚樹脂、含三嗪骨架酚樹脂。具體而言，可列舉出聯苯型酚樹脂的MEH-7700、MEH-7810、MEH-7851(明和化成股份有限公司製)、萘型酚樹脂的NHN、CBN、GPH(日本化藥股份有限公司製)、SN-170、SN-180、SN-190、SN-475、SN-485、SN-495、SN-375、SN-395(新日鐵化學股份有限公司製)、EXB9500(DIC股份有限公司製)、酚-酚醛樹脂的TD2090(DIC股份有限公司製)、萘醚型酚樹脂的EXB-6000(DIC股份有限公司製)、含三嗪骨架酚樹脂的LA-3018、LA-7052、LA-7054、LA-1356(DIC股份有限公司製)等。此等可使用1種或併用2種以上。 The phenol resin is not particularly limited, and is preferably a biphenyl type phenol tree. A fat, a naphthalene type phenol resin, a phenol-phenolic resin, a naphthene ether type phenol resin, and a triazine skeleton phenol resin. Specifically, MEH-7700, MEH-7810, MEH-7851 (made by Minghe Chemical Co., Ltd.), naphthol type phenol resin, NHN, CBN, and GPH of a biphenyl type phenol resin (Nippon Chemical Co., Ltd.) System), SN-170, SN-180, SN-190, SN-475, SN-485, SN-495, SN-375, SN-395 (manufactured by Nippon Steel Chemical Co., Ltd.), EXB9500 (DIC shares limited) Manufactured by the company, TD2090 (made by DIC Corporation) of phenol-phenolic resin, EXB-6000 (made by DIC Corporation) of naphthene ether type phenol resin, LA-3018, LA-7052 containing triazine skeleton phenol resin LA-7054, LA-1356 (manufactured by DIC Corporation). These may be used alone or in combination of two or more.

SN-485的結構式如下列式(4)所示。 The structural formula of SN-485 is as shown in the following formula (4).

(n為1~20為止的整數) (n is an integer from 1 to 20)

此外，LA-7054的結構式如下列式(5)所示。 Further, the structural formula of LA-7054 is as shown in the following formula (5).

(n為1~20為止的整數) (n is an integer from 1 to 20)

氰酸酯樹脂並無特別限制，可列舉出酚醛型氰酸酯樹脂、二環戊二烯型氰酸酯樹脂、雙酚型氰酸酯樹脂、及此等之一部分經三嗪化的預聚物等。具體而言，可列舉出由下列式(6)表示之酚-酚醛型多官能氰酸酯樹脂(Lonza Japan股份有限公司製、PT30S：數量平均分子量380、PT60：數量平均分子量560)、由下列式(7)表示之雙酚A型氰酸酯樹脂的一部分或全部經三嗪化而成為三聚物之預聚物的雙酚A型氰酸酯樹脂(Lonza Japan股份有限公司製、BA230S75)、由下列式(8)表示之二環戊二烯型氰酸酯樹脂(Lonza Japan股份有限公司製、DT-4000、DT-7000)等。具體而言，數量平均分子量，可使用島津製作所股份有限公司製LC-9A/RID-6A作為測定裝置，使用昭和電工股份有限公司製Shodex K-800P/K-804L/K-804L作為管柱，使用三氯甲烷作為移動相，於管柱溫度40℃進行測定，並使用標準聚苯乙烯檢量線來算 出。此等可使用1種或組合2種以上使用。 The cyanate resin is not particularly limited, and examples thereof include a novolac type cyanate resin, a dicyclopentadiene type cyanate resin, a bisphenol type cyanate resin, and a part of the triazine-based prepolymerization. Things and so on. Specifically, a phenol-phenolic polyfunctional cyanate resin (manufactured by Lonza Japan Co., Ltd., PT30S: number average molecular weight 380, PT60: number average molecular weight 560) represented by the following formula (6), and the following A bisphenol A type cyanate resin which is a part of or all of the bisphenol A type cyanate resin represented by the formula (7) and which is a prepolymer of a trimer (Lonza Japan Co., Ltd., BA230S75) A dicyclopentadiene type cyanate resin (manufactured by Lonza Japan Co., Ltd., DT-4000, DT-7000) represented by the following formula (8). Specifically, for the number average molecular weight, LC-9A/RID-6A manufactured by Shimadzu Corporation can be used as a measuring device, and Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. can be used as a column. Use chloroform as the mobile phase, measure at a column temperature of 40 ° C, and use a standard polystyrene calibration line to calculate Out. These may be used alone or in combination of two or more.

[式中，n表示任意數作為平均值之(佳為0~20，較佳為1~10)] [wherein, n represents an arbitrary number as an average value (preferably 0 to 20, preferably 1 to 10)]

(式中，n表示作為平均值之0~5的數) (where n represents the number of 0 to 5 as the average value)

本發明所能夠使用之活性酯樹脂，為於1分 子中具有1個以上的活性酯基之樹脂化合物。在此，所謂「活性酯基」，係意味者可與環氧樹脂反應之酯基。活性酯樹脂，較佳為可與環氧樹脂反應，且於1分子中具有2個以上的活性酯基之樹脂化合物。一般而言，較佳可使用選自由酚酯、硫酚酯、N-羥胺酯及雜環羥基化合物酯所組成之群組，且於1分子中具有2個以上之反應性高的酯基之樹脂化合物，作為活性酯樹脂。活性酯樹脂可使用1種或併用2種以上。 The active ester resin which can be used in the present invention is 1 point A resin compound having one or more active ester groups in the sub-group. Here, the "active ester group" means an ester group which can react with an epoxy resin. The active ester resin is preferably a resin compound which can react with an epoxy resin and has two or more active ester groups in one molecule. In general, it is preferred to use a group selected from the group consisting of phenol esters, thiophenol esters, N-hydroxylamine esters, and heterocyclic hydroxy compound esters, and having two or more highly reactive ester groups in one molecule. A resin compound as an active ester resin. The active ester resin may be used alone or in combination of two or more.

從提升耐熱性之觀點來看，較佳為使羧酸化 合物及/或硫代羧酸化合物，與羥基化合物及/或硫醇化合物進行縮合反應所得到之活性酯樹脂。較佳為選自酚化合物、萘酚化合物及硫醇化合物之1種或2種以上，與羧酸化合物進行反應所得到之活性酯樹脂。更佳為使羧酸化合物與具有酚性羥基之芳香族化合物進行反應所得到，於1分子中具有2個以上的活性酯基之芳香族樹脂化合物。 進一步更佳為使於1分子中具有至少2個以上的羧酸之化合物，與具有酚性羥基之芳香族化合物進行反應所得到之芳香族樹脂化合物，並且為於該芳香族樹脂化合物的1分子中具有2個以上的活性酯基之芳香族樹脂化合物。活性酯樹脂可為直鏈狀或多分枝狀。此外，於1分子中具有至少2個以上的羧酸之化合物，若是包含脂肪族鏈之化合物，則可提高與樹脂組成物之相溶性，若是具有芳香族環之化合物，則可提高耐熱性。 From the viewpoint of improving heat resistance, it is preferred to carry out carboxylation An active ester resin obtained by a condensation reaction of a compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. An active ester resin obtained by reacting one or two or more kinds of a phenol compound, a naphthol compound, and a thiol compound with a carboxylic acid compound is preferred. More preferably, an aromatic resin compound having two or more active ester groups in one molecule is obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group. Furthermore, it is more preferably an aromatic resin compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group, and one molecule of the aromatic resin compound. An aromatic resin compound having two or more active ester groups. The active ester resin may be linear or multi-branched. Further, a compound having at least two or more carboxylic acids in one molecule can improve the compatibility with the resin composition in the case of a compound containing an aliphatic chain, and can improve heat resistance in the case of a compound having an aromatic ring.

上述羧酸化合物，具體可列舉出苯甲酸、乙 酸、琥珀酸、順丁烯二酸、亞甲基丁二酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、焦蜜石酸等。當中，從耐熱性之觀點來看，較佳為琥珀酸、順丁烯二酸、亞甲基丁二酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸，較佳為間苯二甲酸、對苯二甲酸。硫代羧酸化合物，具體可列舉出硫代乙酸、硫代苯甲酸等。 Specific examples of the carboxylic acid compound include benzoic acid and B. Acid, succinic acid, maleic acid, methylene succinic acid, phthalic acid, isophthalic acid, terephthalic acid, pyroic acid, and the like. Among them, from the viewpoint of heat resistance, succinic acid, maleic acid, methylene succinic acid, phthalic acid, isophthalic acid, terephthalic acid, preferably isophthalic acid is preferred. Formic acid, terephthalic acid. Specific examples of the thiocarboxylic acid compound include thioacetic acid and thiobenzoic acid.

上述酚化合物或萘酚化合物，具體可列舉出 對苯二酚、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、苯酚、鄰甲酚、間甲酚、對甲酚、兒茶酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯基酮、三羥基二苯基酮、四羥基二苯基酮、根皮三酚、苯三醇、二環戊二烯二酚、酚-酚醛等。當中，從提升耐熱性、提升溶解性之觀點來看，較佳為雙酚A、雙酚F、雙酚S、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、兒茶酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯基酮、三羥基二苯基酮、四羥基二苯基酮、根皮三酚、苯三醇、二環戊二烯二酚、酚-酚醛，較佳為兒茶酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯基酮、三羥基二苯基酮、四羥基二苯基酮、根皮三酚、苯三醇、二環戊二烯二酚、酚-酚醛，更佳為1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯基酮、三羥基二苯基酮、四羥基二苯基酮、二環戊二烯二酚、酚-酚醛，進一步更佳為1,5-二羥 基萘、1,6-二羥基萘、2,6-二羥基萘、二環戊二烯二酚、酚-酚醛，尤其更佳為1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二環戊二烯二酚，特佳為二環戊二烯二酚。硫醇化合物，具體可列舉出苯二硫醇、三嗪二硫醇等。 The above phenol compound or naphthol compound can be specifically exemplified Hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol , m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxy Phenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, cadaverin, benzenetriol, dicyclopentadiene diol, phenol-phenolic aldehyde, and the like. Among them, from the viewpoint of improving heat resistance and improving solubility, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S are preferred. , catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl Ketone, tetrahydroxydiphenyl ketone, cadaverin, benzenetriol, dicyclopentadiene diol, phenol-phenolic aldehyde, preferably catechol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, cadaverin, benzenetriol, dicyclopentadiene diol, Phenol-phenolic aldehyde, more preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl Ketone, dicyclopentadiene diphenol, phenol-phenolic aldehyde, further preferably 1,5-dihydroxy Ketone, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene diphenol, phenol-phenolic aldehyde, especially preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene 2,6-dihydroxynaphthalene, dicyclopentadiene diphenol, particularly preferably dicyclopentadiene diphenol. Specific examples of the thiol compound include benzenedithiol and triazinedithiol.

作為活性酯樹脂，具體而言，較佳為包含二 環戊二烯二酚結構之活性酯樹脂、包含萘結構之活性酯樹脂、包含酚-酚醛的乙醯化物之活性酯樹脂、包含酚-酚醛的苯甲醯化物之活性酯樹脂，當中較佳為包含萘結構之活性酯樹脂、包含二環戊二烯二酚結構之活性酯樹脂。作為市售品，包含二環戊二烯二酚結構之活性酯樹脂，可列舉出EXB9451、EXB9460、EXB9460S、HPC-8000-65T(DIC股份有限公司製)，包含萘結構之活性酯樹脂，可列舉出EXB9416-70BK(DIC股份有限公司製)，包含酚-酚醛的乙醯化物之活性酯樹脂，可列舉出DC808(三菱化學股份有限公司製)，包含酚-酚醛的苯甲醯化物之活性酯樹脂，可列舉出YLH1026(三菱化學股份有限公司製)等。 As the active ester resin, specifically, it preferably contains two An active ester resin having a cyclopentadiene structure, an active ester resin containing a naphthalene structure, an active ester resin containing a phenol-phenolic acetal compound, and an active ester resin containing a phenol-phenolic benzoic acid halide, among which It is an active ester resin containing a naphthalene structure, and an active ester resin containing a dicyclopentadiene diphenol structure. The commercially available product, the active ester resin containing a dicyclopentadiene diphenol structure, may be EXB9451, EXB9460, EXB9460S, HPC-8000-65T (manufactured by DIC Corporation), and an active ester resin containing a naphthalene structure. The EXB9416-70BK (manufactured by DIC Corporation), and the active ester resin of ethoxylated phenolic phenolic phenol, exemplified by DC808 (manufactured by Mitsubishi Chemical Corporation), and the activity of benzoquinone containing phenol-phenolic aldehyde Examples of the ester resin include YLH1026 (manufactured by Mitsubishi Chemical Corporation).

特佳的活性酯樹脂，為包含由下列式(9) (式中，m為0或1，n的平均值為0.25~1.5，較佳為0.4~1.2)表示之二環戊二烯二酚結構，且於末端具有X-基及XO-基(在此，X可具有取代基之苯基或萘基)之樹脂化合物。該活性酯樹脂的重量平均分子量，佳為 1500~4000，較佳為2000~3000。 A particularly good active ester resin for inclusion in the following formula (9) (wherein m is 0 or 1, n is an average value of 0.25 to 1.5, preferably 0.4 to 1.2) and represents a dicyclopentadiene diphenol structure having an X-group and an XO- group at the terminal (in Thus, a resin compound in which X may have a phenyl group or a naphthyl group of a substituent. The weight average molecular weight of the active ester resin is preferably from 1,500 to 4,000, preferably from 2,000 to 3,000.

更佳的活性酯樹脂，為包含由下列式(10)表示之二環戊二烯二酚結構，且於末端具有X-基及XO-基(在此，X可具有取代基之萘基)，並且重量平均分子量約為2700之活性酯樹脂的HPC-8000-65T。 More preferably, the active ester resin is a dicyclopentadiene diphenol structure represented by the following formula (10), and has an X-group and an XO- group at the terminal (here, X may have a substituent of a naphthyl group) And HPC-8000-65T of an active ester resin having a weight average molecular weight of about 2,700.

(式中，m為0或1，n的平均值為0.4~1.2) (where m is 0 or 1, and the average value of n is 0.4 to 1.2)

本發明之硬化性樹脂組成物中之(C)硬化劑的含量並無特別限定，從同時兼顧絕緣層的低粗糙度化與高撕離強度之觀點來看，該硬化性樹脂組成物中的非揮發成分為100質量%時，佳為3~20質量%，較佳為5~18質量%，更佳為7~15質量%。 The content of the (C) curing agent in the curable resin composition of the present invention is not particularly limited, and the curable resin composition is also considered from the viewpoint of both low roughness and high tear strength of the insulating layer. When the nonvolatile content is 100% by mass, it is preferably from 3 to 20% by mass, preferably from 5 to 18% by mass, and more preferably from 7 to 15% by mass.

此外，環氧樹脂全體的環氧基數為1時，硬化劑的反應基數，佳為0.2~2，較佳為0.3~1.5，更佳為0.4~1。在此，所謂「環氧樹脂全體的環氧基數」，為對於全部的環氧樹脂，將存在於硬化性樹脂組成物中之各環氧樹脂的固體成分質量除以環氧當量之值予以合計後之值。此外，所謂「反應基」，係意味著可與環氧基反應之官能基，所謂「反應基數」，為將以反應基當量除上存在於樹脂組成物中之硬化劑的固體成分質量之值予以合計後之值。 Further, when the number of epoxy groups in the entire epoxy resin is 1, the number of reactive groups of the curing agent is preferably 0.2 to 2, preferably 0.3 to 1.5, more preferably 0.4 to 1. Here, the "number of epoxy groups in the entire epoxy resin" is obtained by dividing the solid content of each epoxy resin present in the curable resin composition by the value of the epoxy equivalent for all the epoxy resins. After the value. In addition, the "reactive group" means a functional group reactive with an epoxy group, and the "reaction group number" is a value obtained by dividing the equivalent of the reaction group by the mass of the solid component of the hardener present in the resin composition. The value after the total is added.

(D)無機填料 (D) inorganic filler

本發明所能夠使用之無機填料，例如可列舉出二氧化矽、氧化鋁、雲母、雲母、矽酸鹽、硫酸鋇、氫氧化鎂、氧化鈦等，較佳為二氧化矽、氧化鋁，特佳為非定形二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二氧化矽、中空二氧化矽、球狀二氧化矽等，較佳為球狀二氧化矽、熔融二氧化矽。從提升無機填料相對於包含硬化性樹脂組成物之本發明之薄片狀層合材料的填充性之觀點來看，更佳為球狀熔融二氧化矽。可使用1種或2種以上的無機填料。市售的球狀熔融二氧化矽，可列舉出Admatechs股份有限公司製「SOC2」、「SOC1」。 Examples of the inorganic filler which can be used in the present invention include cerium oxide, aluminum oxide, mica, mica, ceric acid salt, barium sulfate, magnesium hydroxide, titanium oxide, etc., and preferably cerium oxide or aluminum oxide. Preferably, it is amorphous cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, hollow cerium oxide, spherical cerium oxide, etc., preferably spherical cerium oxide or molten cerium oxide. From the viewpoint of enhancing the filling property of the inorganic filler with respect to the sheet-like laminate of the present invention containing the curable resin composition, it is more preferable to be spherical molten cerium oxide. One type or two or more types of inorganic fillers can be used. Commercially available spherical molten cerium oxide is exemplified by "SOC2" and "SOC1" manufactured by Admatech Co., Ltd.

無機填料的平均粒徑並無特別限定，從在絕 緣層上形成細微配線之觀點來看，佳為5μm以下，較佳為3μm以下，更佳為1μm以下，進一步更佳為0.8μm以下，特別更佳為0.6μm以下。另一方面，在將硬化性樹脂組成物形成為清漆時，從防止清漆的黏度上升而使處理性降低之觀點來看，佳為0.01μm以上，較佳為0.03μm以上，更佳為0.07μm以上，進一步更佳為0.1μm以上。上述無機填料的平均粒徑，可藉由依據米氏(Mie)散射理論之雷射繞射散射法來測定。具體而言，可藉由雷射繞射散射型粒度分布測定裝置，以體積基準製作出無機填料的粒度分布，並以該中位徑作為平均粒徑。 測定樣本，較佳係使用藉由超音波於水中使無機填料分散者。雷射繞射散射型粒度分布測定裝置，可使用堀場製作 所股份有限公司製LA-950等。 The average particle diameter of the inorganic filler is not particularly limited, and From the viewpoint of forming fine wiring on the edge layer, it is preferably 5 μm or less, preferably 3 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, and still more preferably 0.6 μm or less. On the other hand, when the curable resin composition is formed into a varnish, it is preferably 0.01 μm or more, preferably 0.03 μm or more, and more preferably 0.07 μm from the viewpoint of preventing the viscosity of the varnish from increasing and improving the handleability. More preferably, it is 0.1 micrometer or more. The average particle diameter of the above inorganic filler can be measured by a laser diffraction scattering method according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced on a volume basis by a laser diffraction scattering type particle size distribution measuring apparatus, and the median diameter is used as the average particle diameter. The sample is preferably measured by using an ultrasonic wave to disperse the inorganic filler in water. Laser diffraction scattering type particle size distribution measuring device, which can be produced by open field LA-950, etc. of the company.

無機填料的含量並無特別限制，從防止薄片 狀層合材料之薄片形態的可撓性降低之觀點來看，硬化性樹脂組成物中的非揮發成分為100質量%時，無機填料的量佳為30~90質量%，較佳為40~85質量%，更佳為50~85質量%。尤其在本發明中，即使在包含50質量%以上的無機填料之硬化性樹脂組成物中，亦可提升撕離強度。 The content of the inorganic filler is not particularly limited, from the prevention of the sheet When the non-volatile component in the curable resin composition is 100% by mass, the amount of the inorganic filler is preferably from 30 to 90% by mass, preferably 40%, from the viewpoint of the flexibility of the sheet form of the laminate. 85 mass%, more preferably 50-8 mass%. In particular, in the present invention, the peeling strength can be improved even in a curable resin composition containing 50% by mass or more of the inorganic filler.

為了提升無機填料的耐濕性、分散性，較佳 為藉由偶合劑等進行表面處理(施以塗膜)。作為表面處理劑(偶合劑)，佳為選自環氧矽烷系偶合劑、胺基矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、有機矽氮烷化合物、鈦酸酯系偶合劑之1種以上。此等當中，胺基矽烷系偶合劑，其耐濕性、分散性、硬化物的特性等為優異，故較佳，較佳為苯基胺基矽烷系偶合劑。市售品可列舉出信越化學股份有限公司製「KBM403」(3-環氧丙氧基丙基三甲氧矽烷)、信越化學股份有限公司製「KBM803」(3-巰基丙基三甲氧矽烷)、信越化學股份有限公司製「KBE903」(3-胺基丙基三乙氧矽烷)、信越化學股份有限公司製「KBM573」(N-苯基-3-胺基丙基三甲氧矽烷)、信越化學股份有限公司製「KBM103」(苯基三甲氧矽烷)、信越化學股份有限公司製「SZ-31」(六甲基二矽氮烷)等。 In order to improve the moisture resistance and dispersibility of the inorganic filler, it is preferred The surface treatment (application of a coating film) is carried out by a coupling agent or the like. The surface treatment agent (coupling agent) is preferably selected from the group consisting of an epoxy decene coupling agent, an amino decane coupling agent, a decyl decane coupling agent, a decane coupling agent, an organic decane compound, and a titanate coupling agent. One or more of them. Among these, the amino decane-based coupling agent is preferred because it is excellent in moisture resistance, dispersibility, and properties of a cured product, and is preferably a phenylamino decane-based coupling agent. "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxy decane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxy decane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyl trimethoxane) manufactured by Seiko Co., Ltd., "SZ-31" (hexamethyldioxane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

[其他成分] [Other ingredients]

本發明之硬化性樹脂組成物中，除了上述成分之外，作為其他成分，亦可適當地調配：硬化促進劑；熱塑性樹脂；乙烯基苄化合物、丙烯酸化合物、順丁烯二醯亞胺化合物、封端化異氰酸酯化合物般之熱硬化性樹脂；磷系化合物、氫氧化金屬物等之難燃劑；矽粉末、尼龍粉末、氟粉末、橡膠粒子等之有機填料；有機溶劑；有機皂土、皂土等之增黏劑；聚矽氧系、氟系、高分子系的消泡劑；咪唑系、噻唑系、***系、矽烷偶合劑等之密著性賦予劑；酞菁藍、酞菁綠、碘綠、雙偶氮黃、碳黑等之著色劑；添加劑等。 In addition to the above components, the curable resin composition of the present invention may be appropriately formulated as a curing component, a curing accelerator, a thermoplastic resin, a vinyl benzyl compound, an acrylic compound, a maleimide compound, or the like. a thermosetting resin such as a blocked isocyanate compound; a flame retardant such as a phosphorus compound or a metal hydroxide; an organic filler such as barium powder, nylon powder, fluorine powder or rubber particles; organic solvent; organic bentonite and soap Adhesives such as earth; polyfluorene, fluorine, and polymer defoamers; adhesion imparting agents such as imidazole, thiazole, triazole, and decane coupling agents; phthalocyanine blue, phthalocyanine A coloring agent such as green, iodine green, disazo yellow, carbon black, etc.; additives, and the like.

硬化促進劑，只要是可促進上述硬化劑對上 述環氧樹脂所進行之交聯及硬化者，則任意硬化促進劑均可使用，例如可列舉出胺化合物、胍化合物、咪唑化合物、鏻鹽化合物及金屬系硬化促進劑等。此等可使用1種或組合2種以上使用。 a hardening accelerator as long as it promotes the above-mentioned hardener Any of the curing accelerators may be used for the crosslinking and curing of the epoxy resin, and examples thereof include an amine compound, an anthracene compound, an imidazole compound, an onium salt compound, and a metal-based curing accelerator. These may be used alone or in combination of two or more.

本發明所能夠使用之胺化合物並無特別限 定，可列舉出三乙胺、三丁胺等之三烷胺、4-二甲基胺基吡啶(DMAP)、苄基二甲胺、2,4,6-三(二甲基胺甲基)酚、1,8-二偶氮雙環(5,4,0)-十一烯(以下略記為DBU)等之胺化合物等。此等可使用1種或組合2種以上使用。 The amine compound which can be used in the present invention is not particularly limited The trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, and 2,4,6-tris(dimethylaminomethyl) An amine compound such as phenol or 1,8-diazobicyclo(5,4,0)-undecene (hereinafter abbreviated as DBU). These may be used alone or in combination of two or more.

本發明所能夠使用之咪唑化合物，可為由下 列一般式(11) (式中，R6~R9可互為相同或相異，為氫原子、鹵素原子、氰基、硝基、甲醯基、C1-20烷基、C2-20烯基、C2-20炔基、C3-20烯丙基、C4-20烷二烯基、C4-20多烯基、C6-20芳基、C6-20烷芳基、C6-20芳烷基、C4-20環烷基、C4-20環烯基、(C5-10環烷基)C1-10烷基、可具有C1-10烴基之矽烷基、來自環氧樹脂之羥乙基)表示之化合物。 The imidazole compound which can be used in the present invention can be represented by the following general formula (11) (wherein R 6 to R 9 may be the same or different from each other, and are a hydrogen atom, a halogen atom, a cyano group, a nitro group, a decyl group, a C 1-20 alkyl group, a C 2-20 alkenyl group, a C 2 group ; -20 alkynyl, C 3-20 allyl, C 4-20 alkadienyl, C 4-20 polyalkenyl , C 6-20 aryl, C 6-20 alkaryl, C 6-20 aryl Alkyl, C 4-20 cycloalkyl, C 4-20 cycloalkenyl, (C 5-10 cycloalkyl) C 1-10 alkyl, decyl group which may have a C 1-10 hydrocarbyl group, derived from an epoxy resin The compound represented by hydroxyethyl).

具體而言，咪唑化合物，可為選自由1-苄基-2-苯基咪唑、2-乙基-4-甲基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-十一基咪唑、1-氰乙基-2-苯基咪唑、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-三嗪三聚異氰酸加成物、2-苯基咪唑三聚異氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4甲基-5-羥甲基咪唑、2-苯基-4甲基咪唑、咪唑化合物與環氧樹脂之加成物以及2,4-二胺基-6-乙烯基-S-三嗪所組成之群組的化合物。此等可使用1種或組合2種以上使用。 Specifically, the imidazole compound may be selected from the group consisting of 1-benzyl-2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]- Ethyl-S-triazine, 2,4-diamino-6-[2'-undecidamidazolyl-(1')]-ethyl-S-triazine, 2,4-diamino- 6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-S-triazine, 2,4-diamino-6-[2'-methylimidazolyl- (1')]-Ethyl-S-triazine trimeric isocyanate adduct, 2-phenylimidazole trimeric isocyanate adduct, 2-phenyl-4,5-dihydroxymethylimidazole , 2-phenyl-4methyl-5-hydroxymethylimidazole, 2-phenyl-4methylimidazole, adduct of imidazole compound and epoxy resin, and 2,4-diamino-6-vinyl a compound of the group consisting of -S-triazine. These may be used alone or in combination of two or more.

本發明所能夠使用之金屬系硬化促進劑並無特別限定，可列舉出鈷、銅、鋅、鐵、鎳、錳、錫等之金屬的有機金屬錯合物或有機金屬鹽。作為有機金屬錯合物 的具體例，可列舉出鈷(II)乙醯丙酮酸、鈷(III)乙醯丙酮酸等之有機鈷錯合物、銅(II)乙醯丙酮酸等之有機銅錯合物、鋅(II)乙醯丙酮酸等之有機鋅錯合物、鐵(III)乙醯丙酮酸等之有機鐵錯合物、鎳(II)乙醯丙酮酸等之有機鎳錯合物、錳(II)乙醯丙酮酸等之有機錳錯合物等。作為有機金屬鹽，可列舉出辛酸鋅、辛酸錫、環烷酸鋅、環烷酸鈷、硬脂酸錫、硬脂酸鋅等。此等可使用1種或組合2種以上使用。 The metal-based curing accelerator which can be used in the present invention is not particularly limited, and examples thereof include organometallic complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Organometallic complex Specific examples thereof include organic cobalt complexes such as cobalt (II) acetoacetate, cobalt (III) acetoacetate, and organic copper complexes such as copper (II) acetoacetate, and zinc ( II) an organic zinc complex such as acetylpyruvate, an organic iron complex such as iron (III) acetoacetate, an organic nickel complex such as nickel (II) acetoacetate, or manganese (II) An organic manganese complex such as acetoacetic acid or the like. Examples of the organic metal salt include zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.

硬化促進劑的含量，硬化性樹脂組成物中的 非揮發成分的合計為100質量%時，佳為在0.005~3質量%的範圍內使用，較佳為在0.01~1質量%的範圍內使用。 The content of the hardening accelerator in the curable resin composition When the total amount of the nonvolatile components is 100% by mass, it is preferably used in the range of 0.005 to 3% by mass, and preferably used in the range of 0.01 to 1% by mass.

作為熱塑性樹脂，在不阻礙本發明的效果之 程度下，例如可列舉出(A)具有茀結構之苯氧樹脂以外的苯氧樹脂、聚乙烯縮醛樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚碸樹脂、環烯烴聚合物及聚碸樹脂等，較佳為聚乙烯縮醛樹脂。此等可使用1種或組合2種以上使用。 As the thermoplastic resin, the effect of the present invention is not hindered To the extent, for example, (A) a phenoxy resin other than a phenoxy resin having a fluorene structure, a polyvinyl acetal resin, a polyimine resin, a polyamidoximine resin, a polyether oxime resin, a cycloolefin The polymer, the polyfluorene resin and the like are preferably a polyvinyl acetal resin. These may be used alone or in combination of two or more.

熱塑性樹脂之經聚苯乙烯換算的重量平均分 子量，佳為8000~70000的範圍，較佳為10000~60000的範圍，更佳為20000~60000的範圍。熱塑性樹脂之經聚苯乙烯換算的重量平均分子量，與(A)苯氧樹脂之重量平均分子量的測定方法相同，可藉由凝膠滲透層析(GPC)法來測定。 Polystyrene-equivalent weight average of thermoplastic resin The sub-quantity is preferably in the range of 8000 to 70,000, preferably in the range of 10,000 to 60,000, more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is the same as the method for measuring the weight average molecular weight of the (A) phenoxy resin, and can be measured by a gel permeation chromatography (GPC) method.

有機溶劑，例如可列舉出丙酮、丁酮、環己 酮等之酮類；乙酸乙酯、乙酸丁酯、溶纖劑乙酸酯、丙二醇單甲醚乙酸酯、卡必醇乙酸酯等之乙酸酯類；溶纖劑、丁基卡必醇等之卡必醇類；溶劑油、甲苯、二甲苯等之芳香族烴類；二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮等之醯胺系溶劑等。有機溶劑可組合2種以上使用。 Examples of the organic solvent include acetone, methyl ethyl ketone, and cyclohexane. Ketones such as ketones; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate; cellosolve, butyl carbitol Such as carbitol; aromatic hydrocarbons such as solvent oil, toluene, and xylene; and guanamine solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Two or more types of organic solvents can be used in combination.

[硬化性樹脂組成物的調製] [Modulation of Curable Resin Composition]

本發明之硬化性樹脂組成物，可適當地混合上述成分，且因應必要藉由三軋輥、球磨機、珠磨機、砂磨機等之混練手段，或是高速旋轉混合機、超級混合機、行星式混合機等之攪拌手段進行混練或混合而調製出。此外，亦可進一步加入上述有機溶劑而調製成樹脂清漆。 The curable resin composition of the present invention can be appropriately mixed with the above components, and if necessary, by a kneading method such as a three-roller, a ball mill, a bead mill, a sand mill, or the like, or a high-speed rotary mixer, a super mixer, or a planet. A stirring means such as a mixer is kneaded or mixed to prepare a mixture. Further, the above organic solvent may be further added to prepare a resin varnish.

本發明之硬化性樹脂組成物中，不僅絕緣層 表面的算術平均粗糙度低，且均方根粗糙度低，於該上方可形成具有充分的撕離強度之電鍍導體層，所以在多層印刷配線板的製造中，可適合地使用作為多層印刷配線板之絕緣層用硬化性樹脂組成物。此外，可適合地使用作為用以藉由電鍍來形成導體層之硬化性樹脂組成物(藉由電鍍形成導體層之多層印刷配線板之絕緣層用樹脂組成物)，再者，亦可適合地使用作為多層印刷配線板之增層用硬化性樹脂組成物。 In the curable resin composition of the present invention, not only the insulating layer Since the arithmetic mean roughness of the surface is low and the root mean square roughness is low, an electroplated conductor layer having sufficient tear strength can be formed on the upper surface, so that it can be suitably used as a multilayer printed wiring in the manufacture of a multilayer printed wiring board. A hardening resin composition for the insulating layer of the board. In addition, a curable resin composition for forming a conductor layer by electroplating (a resin composition for an insulating layer of a multilayer printed wiring board in which a conductor layer is formed by electroplating) can be suitably used, and further, suitably A curable resin composition for a build-up layer of a multilayer printed wiring board is used.

本發明之硬化性樹脂組成物的形態並無特別 限定，可適用於黏著薄膜、預浸體等之薄片狀層合材料、 電路基板(層合板用途、多層印刷配線板用途等)。本發明之樹脂組成物，亦可以清漆狀態塗佈於電路基板以形成絕緣層，但工業上一般較佳是以黏著薄膜、預浸體等之薄片狀層合材料的形態來使用。樹脂組成物的軟化點，從薄片狀層合材料的疊合性之觀點來看，較佳為40~150℃。 The form of the curable resin composition of the present invention is not particularly Limited, it can be applied to sheet laminates such as adhesive films and prepregs, Circuit board (for laminate use, multilayer printed wiring board use, etc.). The resin composition of the present invention may be applied to a circuit board in a varnish state to form an insulating layer. However, it is generally used in the form of a sheet-like laminate such as an adhesive film or a prepreg. The softening point of the resin composition is preferably from 40 to 150 ° C from the viewpoint of the lamination property of the sheet-like laminate.

[多層印刷配線板] [Multilayer printed wiring board]

本發明之硬化性樹脂組成物，可使用作為多層印刷配線板之絕緣層用硬化性樹脂組成物。本發明所能夠使用之多層印刷配線板，為包含使本發明之硬化性樹脂組成物或薄片狀層合材料熱硬化而得到之絕緣層之多層印刷配線板。 As the curable resin composition of the present invention, a curable resin composition for an insulating layer of a multilayer printed wiring board can be used. The multilayer printed wiring board which can be used in the present invention is a multilayer printed wiring board including an insulating layer obtained by thermally curing the curable resin composition or the sheet-like laminate of the present invention.

在此，熱硬化的條件，可因應硬化性樹脂組成物中之環氧樹脂的種類、含量等來適當地選擇，例如可在硬化溫度為90~220℃，更佳為160℃~210℃，硬化時間為10分鐘~180分鐘，較佳為20分鐘~120分鐘之加熱下進行。此外，亦可分成2階段來進行熱硬化。 Here, the conditions of the heat curing can be appropriately selected depending on the type and content of the epoxy resin in the curable resin composition, and for example, the curing temperature is 90 to 220 ° C, more preferably 160 ° C to 210 ° C. The hardening time is from 10 minutes to 180 minutes, preferably from 20 minutes to 120 minutes. In addition, it can be divided into two stages for thermal hardening.

在此，絕緣層的線熱膨脹係數(CTE)(JIS K7197)，是由25~150℃的平均線熱膨脹係數來測定，較佳為20ppm/℃以下，更佳為19ppm/℃以下。下限值並無特別限制，一般為4ppm/℃。藉此，防止絕緣層(增層)與導體層(配線)之扭曲，而能夠得到可靠度高之多層印刷配線板。 Here, the linear thermal expansion coefficient (CTE) (JIS K7197) of the insulating layer is measured by an average linear thermal expansion coefficient of 25 to 150 ° C, preferably 20 ppm / ° C or less, more preferably 19 ppm / ° C or less. The lower limit is not particularly limited and is generally 4 ppm/°C. Thereby, the insulating layer (growth layer) and the conductor layer (wiring) are prevented from being twisted, and a multilayer printed wiring board having high reliability can be obtained.

絕緣層表面可進行粗化處理。作為式粗化處 理可列舉出電漿處理等。濕式粗化處理，例如可藉由適用各種處理液來進行。可列舉出依序進行膨潤液的膨潤處理、氧化劑的粗化處理及中和液的中和處理之方法。因此，處理液可為此等膨潤液、氧化劑、中和液的組合液。 濕式粗化處理者，就可一次處理大面積或複數片且生產性高之方面來看為較佳。 The surface of the insulating layer can be roughened. Roughing The plasma treatment and the like can be cited. The wet roughening treatment can be carried out, for example, by applying various treatment liquids. A method of sequentially performing a swelling treatment of a swelling liquid, a roughening treatment of an oxidizing agent, and a neutralization treatment of a neutralizing liquid can be mentioned. Therefore, the treatment liquid can be a combination of such a swelling liquid, an oxidizing agent, and a neutralizing liquid. The wet roughening processor is preferable in that it can process a large area or a plurality of sheets at a time and is highly productive.

膨潤液的膨潤處理，係在50~80℃、5~20分鐘(較佳為55~70℃、8~15分鐘)下，將絕緣層浸漬在膨潤液而進行。膨潤液例如可列舉出鹼溶液、界面活性劑溶液等，較佳為鹼溶液。該鹼溶液例如可列舉出氫氧化鈉溶液、氫氧化鉀溶液等。作為市售的膨潤液，例如可列舉出Atotech Japan股份有限公司製的Swelling Dip Securiganth P、Swelling Dip Securiganth SBU等。 The swelling treatment of the swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50 to 80 ° C for 5 to 20 minutes (preferably 55 to 70 ° C for 8 to 15 minutes). Examples of the swelling liquid include an alkali solution, a surfactant solution, and the like, and an alkali solution is preferred. Examples of the alkali solution include a sodium hydroxide solution, a potassium hydroxide solution, and the like. As a commercially available swelling liquid, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU, etc. by Atotech Japan Co., Ltd., etc. are mentioned, for example.

藉由氧化劑的粗化處理，係在60~80℃、10~30分鐘(較佳為70~80℃、15~25分鐘)下，將絕緣層浸漬在氧化劑溶液而進行。作為氧化劑例如可列舉出將過錳酸鉀或過錳酸鈉溶解於氫氧化鈉水溶液之鹼性過錳酸溶液、重鉻酸鹽、臭氧、過氧化氫/硫酸、硝酸等。此外，鹼性過錳酸溶液中之過錳酸鹽的濃度，佳為5~10質量%。作為市售的氧化劑，例如可列舉出Atotech Japan股份有限公司製的Concentrate Compact CP、Dosing Solution Securiganth P等之鹼性過錳酸溶液。 The oxidizing agent is immersed in an oxidizing agent solution at 60 to 80 ° C for 10 to 30 minutes (preferably 70 to 80 ° C for 15 to 25 minutes). Examples of the oxidizing agent include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, or the like. Further, the concentration of the permanganate in the alkaline permanganic acid solution is preferably from 5 to 10% by mass. The commercially available oxidizing agent is, for example, an alkaline permanganic acid solution such as Concentrate Compact CP or Dosing Solution Securiganth P manufactured by Atotech Japan Co., Ltd.

藉由中和液的中和處理，係在30~50℃、3~10分鐘(較佳為35~45℃、3~8分鐘)下浸漬在中和液而進行。 作為中和液佳為酸性水溶液，市售品可列舉出Atotech Japan股份有限公司製的Reduction Solution Sccuriganth P。 The neutralization treatment by the neutralization solution is carried out by immersing in a neutralizing solution at 30 to 50 ° C for 3 to 10 minutes (preferably 35 to 45 ° C for 3 to 8 minutes). The neutralizing liquid is preferably an acidic aqueous solution, and a commercially available product is Reduction Solution Sccuriganth P manufactured by Atotech Japan Co., Ltd.

粗化處理後，可在50~120℃、10~60分鐘(較佳為60~100℃、20~40分鐘)下將絕緣層乾燥。 After the roughening treatment, the insulating layer may be dried at 50 to 120 ° C for 10 to 60 minutes (preferably 60 to 100 ° C, 20 to 40 minutes).

粗化處理後之絕緣層表面的表面粗糙度，為 了提升細微配線的形成，算術平均粗糙度(Ra)佳為350nm以下，較佳為300nm以下，更佳為200nm以下，特佳為100nm以下。算術平均粗糙度(Ra)的下限值並無特別限定，一般為10nm以上、40nm以上、70nm以上等。均方根粗糙度(Rq)佳為450nm以下，較佳為350nm以下，更佳為250nm以下，特佳為150nm以下。 均方根粗糙度(Rq)的下限值並無特別限定，一般為20nm以上、50nm以上、90nm以上等。由於均方根粗糙度(Rq)反映出絕緣層表面的局部狀態，故可藉由掌握Rq來確認有沒成為緊緻且平滑的絕緣層表面，而使撕離強度達到穩定化。此係相當於使硬化性樹脂組成物熱硬化並進行粗化處理後之絕緣層的表面粗糙度。 The surface roughness of the surface of the insulating layer after roughening treatment is In order to improve the formation of the fine wiring, the arithmetic mean roughness (Ra) is preferably 350 nm or less, preferably 300 nm or less, more preferably 200 nm or less, and particularly preferably 100 nm or less. The lower limit of the arithmetic mean roughness (Ra) is not particularly limited, but is generally 10 nm or more, 40 nm or more, 70 nm or more. The root mean square roughness (Rq) is preferably 450 nm or less, preferably 350 nm or less, more preferably 250 nm or less, and particularly preferably 150 nm or less. The lower limit of the root mean square roughness (Rq) is not particularly limited, but is generally 20 nm or more, 50 nm or more, 90 nm or more. Since the root mean square roughness (Rq) reflects the local state of the surface of the insulating layer, it is possible to confirm the presence or absence of a firm and smooth surface of the insulating layer by grasping Rq, and to stabilize the tear strength. This corresponds to the surface roughness of the insulating layer after the hardening resin composition is thermally cured and roughened.

撕離強度，係為了充分地使絕緣層與鄰接的 層，例如與導體層密著，佳為0.45kgf/cm(4.41N/cm)以上，較佳為0.50kgf/cm(4.90N/cm)以上。撕離強度的上限值愈高愈佳，並無特別限制，一般為1.5kgf/cm(14.7N/cm)以下，1.2kgf/cm(11.8N/cm)以下，1.0kgf/cm(9.81N/cm)以下，0.8kgf/cm(7.85N/cm)以 下等。 Peeling strength, in order to fully make the insulation layer adjacent The layer is, for example, adhered to the conductor layer, preferably 0.45 kgf/cm (4.41 N/cm) or more, preferably 0.50 kgf/cm (4.90 N/cm) or more. The upper limit of the tear strength is preferably higher, and is not particularly limited, and is generally 1.5 kgf/cm (14.7 N/cm) or less, 1.2 kgf/cm (11.8 N/cm) or less, and 1.0 kgf/cm (9.81 N). /cm) below, 0.8kgf/cm (7.85N/cm) inferior.

破壞點伸長度，係依據JIS K7127來測定使硬 化性樹脂組成物熱硬化而得到之硬化物的拉伸強度。具體而言，可製作出從該硬化物裁切成啞鈴狀之試驗片，剝離PET薄膜，並使用Orientec公司製拉伸試驗機RTC-1250A來測定。破壞點伸長度較佳為1.5%以上，更佳為1.7%以上。 Destruction point elongation, measured according to JIS K7127 to make hard The tensile strength of the cured product obtained by thermosetting the chemical resin composition. Specifically, a test piece cut into a dumbbell shape from the cured product was produced, and the PET film was peeled off and measured using a tensile tester RTC-1250A manufactured by Orientec. The breaking point elongation is preferably 1.5% or more, more preferably 1.7% or more.

[薄片狀層合材料] [Sheet laminate]

本發明中所使用之薄片狀層合材料，為將上述硬化性樹脂組成物形成為層，且為硬化前之薄片狀材料。該薄片狀層合材料，可藉由該業者所熟知的方法，例如調製出使樹脂組成物溶解於上述有機溶劑之樹脂清漆，並使用壓模塗佈機等將該樹脂清漆塗佈於支撐體上，然後藉由加熱或是熱風吹送等使有機溶劑乾燥，而在支撐體上形成樹脂組成物層(薄片狀層合材料)，藉此可製造作為附有支撐體之薄片狀層合材料。此外，可藉由熱熔法或溶劑法使樹脂清漆含浸於玻璃布等之薄片狀補強基材並乾燥，藉此可將薄片狀層合材料形成為預浸體。有時亦有將附有支撐體之薄片狀層合材料稱為黏著薄膜的情形。 The sheet-like laminate used in the present invention is a sheet-like material in which the curable resin composition is formed into a layer and is cured. In the sheet-like laminate, a resin varnish in which a resin composition is dissolved in the organic solvent can be prepared by a method known to those skilled in the art, and the resin varnish can be applied to a support by a die coater or the like. Then, the organic solvent is dried by heating or hot air blowing, and a resin composition layer (sheet-like laminate) is formed on the support, whereby a sheet-like laminate which is provided with a support can be produced. Further, the resin varnish can be impregnated into a sheet-like reinforcing substrate such as glass cloth by a hot melt method or a solvent method, and dried, whereby the sheet-like laminate can be formed into a prepreg. There are cases where a sheet-like laminate material with a support is sometimes referred to as an adhesive film.

乾燥條件並無特別限定，佳為使有機溶劑於 樹脂組成物層中的含量成為10質量%以下，較佳成為5質量%以下之方式進行乾燥。清漆中的有機溶劑量，因有機溶劑之沸點的不同而有所不同，例如可在50~150℃使 包含30~60質量%的有機溶劑之清漆乾燥約3~10分鐘而藉此形成樹脂組成物層。 The drying conditions are not particularly limited, and it is preferred to use an organic solvent. The content in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. The amount of organic solvent in the varnish varies depending on the boiling point of the organic solvent, for example, it can be made at 50 to 150 ° C. The varnish containing 30 to 60% by mass of the organic solvent is dried for about 3 to 10 minutes to form a resin composition layer.

得到之薄片狀層合材料的厚度並無特別限定，例如佳為1~150μm的範圍，較佳為2~100μm的範圍，更佳為3~50μm的範圍，特佳為5~30μm的範圍。 The thickness of the obtained sheet-like laminate is not particularly limited, and is, for example, preferably in the range of 1 to 150 μm, preferably in the range of 2 to 100 μm, more preferably in the range of 3 to 50 μm, and particularly preferably in the range of 5 to 30 μm.

該薄片狀層合材料，樹脂組成物層可層合複數層，亦可於樹脂組成物層之一方的面具有支撐體，或是於另一方的面具有保護薄膜。 In the sheet-like laminate, the resin composition layer may be laminated with a plurality of layers, or may have a support on one side of the resin composition layer or a protective film on the other side.

[支撐體] [support]

本發明中所使用之支撐體，可列舉出塑膠薄膜或金屬箔。具體而言，作為塑膠薄膜可列舉出聚對苯二甲酸乙二酯(以下有時略稱為「PET」)、聚萘二甲酸乙二酯等之聚酯、聚碳酸酯、聚乙烯、聚丙烯、丙烯酸、環狀聚烯烴、三乙醯纖維素、聚醚硫化物、聚醚酮、聚醯亞胺等。當中佳為聚對苯二甲酸乙二酯薄膜、聚萘二甲酸乙二酯薄膜，較佳為便宜且容易取得之聚對苯二甲酸乙二酯薄膜。 The support used in the present invention may, for example, be a plastic film or a metal foil. Specifically, examples of the plastic film include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyester such as polyethylene naphthalate, polycarbonate, polyethylene, and poly. Propylene, acrylic acid, cyclic polyolefin, triacetyl cellulose, polyether sulfide, polyether ketone, polyimine, and the like. Among them, a polyethylene terephthalate film or a polyethylene naphthalate film is preferably a polyethylene terephthalate film which is inexpensive and easily available.

作為金屬箔可列舉出銅箔、鋁箔等。 Examples of the metal foil include a copper foil, an aluminum foil, and the like.

從泛用性之觀點來看，較佳為塑膠薄膜，當使用塑膠薄膜時，為了提升剝離性，較佳係使用與包含硬化性樹脂組成物之層接觸的一面進行脫模處理後之支撐體。脫模處理所使用之脫模劑，只要是可使包含硬化性樹脂組成物之層從支撐體剝離者即可，並無特別限定，例如可列舉出矽系脫模劑、醇酸樹脂系脫模劑、聚烯烴樹脂、 胺甲酸乙酯樹脂、氟樹脂等。尚且脫模處理後之支撐體，可使用市售之附脫模層之塑膠薄膜。較佳者，例如可列舉出具有以醇酸樹脂系脫模劑為主成分之脫模層之PET薄膜的SK-1、AL-5、AL-7(Lintec股份有限公司製)等。 此外，塑膠薄膜可施以消光處理或電暈處理，並於該處理面上形成脫模層。另一方面，金屬箔亦可藉由蝕刻溶液來去除，或是不去除而將該金屬箔用作為導體層。 From the viewpoint of versatility, it is preferably a plastic film. When a plastic film is used, in order to improve the peeling property, it is preferred to use a support which is subjected to release treatment after being in contact with the layer containing the layer of the curable resin composition. . The release agent to be used for the release treatment is not particularly limited as long as the layer containing the curable resin composition can be peeled off from the support, and examples thereof include a oxime release agent and an alkyd resin release agent. Molding agent, polyolefin resin, A urethane resin, a fluororesin, or the like. Further, a commercially available release plastic film with a release layer can be used as the support after the release treatment. For example, SK-1, AL-5, AL-7 (manufactured by Lintec Co., Ltd.) having a PET film having a release layer containing an alkyd-based release agent as a main component is exemplified. Further, the plastic film may be subjected to a matting treatment or a corona treatment, and a release layer is formed on the treated surface. On the other hand, the metal foil may be removed by an etching solution or may be used as a conductor layer without being removed.

支撐體的厚度並無特別限定，佳為10~150μm的範圍，較佳為20~50μm的範圍，更佳為25~45μm的範圍。 The thickness of the support is not particularly limited, but is preferably in the range of 10 to 150 μm, preferably in the range of 20 to 50 μm, and more preferably in the range of 25 to 45 μm.

本發明中所使用之保護薄膜，亦可基於防止 雜物等附著於包含硬化性樹脂組成物之層之目的來設置。 作為該保護薄膜，可使用與支撐體相同之塑膠薄膜。此外，亦可對保護薄膜施以消光處理、電暈處理等之表面處理，或是施以與上述相同之脫模處理。保護薄膜的厚度，佳為3~30μm，較佳為5~20μm。 The protective film used in the present invention can also be based on prevention The foreign matter or the like is attached for the purpose of adhering to the layer containing the curable resin composition. As the protective film, the same plastic film as the support can be used. Further, the protective film may be subjected to a surface treatment such as matting treatment, corona treatment, or the like, or subjected to the same release treatment as described above. The thickness of the protective film is preferably from 3 to 30 μm, preferably from 5 to 20 μm.

[使用薄片狀層合材料之多層印刷配線板] [Multilayer printed wiring board using sheet laminate]

接著說明使用以上述方式所製造之薄片狀層合材料來製造多層印刷配線板之方法的一例。 Next, an example of a method of manufacturing a multilayer printed wiring board using the sheet-like laminate produced in the above manner will be described.

首先使用真空疊合機，將薄片狀層合材料疊合(層合)於電路基板的單面或雙面。作為電路基板所使用之基板，可列舉出玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚苯醚基板等。在此 所謂電路基板，是指在上述基板的單面或雙面上形成有經圖型加工後的導體層(電路)者。此外，在交互地層合導體層與絕緣層而成之多層印刷配線板中，該多層印刷配線板之最外層的單面或雙面為經圖型加工後的導體層(電路)者，亦包含於在此所謂的電路基板。尚且，於導體層表面，可藉由黑化處理、銅蝕刻等預先施以粗化處理。 First, a laminar laminate is laminated (laminated) on one or both sides of the circuit substrate using a vacuum laminator. Examples of the substrate used for the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. here The circuit board refers to a conductor layer (circuit) formed by patterning on one or both sides of the substrate. Further, in the multilayer printed wiring board in which the conductor layer and the insulating layer are alternately laminated, the one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits), and also include The so-called circuit substrate here. Further, on the surface of the conductor layer, roughening treatment may be applied in advance by blackening treatment, copper etching, or the like.

上述疊合中，當薄片狀層合材料具有保護薄 膜時，在去除該保護薄膜後，可因應必要來預熱薄片狀層合材料及電路基板，一邊將薄片狀層合材料加壓及加熱一邊疊合於電路基板。本發明之薄片狀層合材料中，較佳係採用藉由真空疊合法在減壓下疊合於電路基板之方法。疊合的條件並無特別限定，例如減壓至空氣壓20mmHg(26.7hPa)以下約10~120秒，然後較佳將壓著溫度(疊合溫度)設為70~140℃，將壓著壓力(疊合壓力)設為0.1~1.5MPa，較佳設為0.5~1.2MPa，將壓著時間(疊合時間)設為5~180秒來進行疊合。此外，疊合的方法可為分批式或是依據輥之連續式。真空疊合，可使用市售的真空疊合機來進行。市售的真空疊合機，例如可列舉出Nichigo Morton股份有限公司製Vacuum Applicator、名機製作所股份有限公司製真空加壓式疊合機、Hitachi Industries股份有限公司製輥式乾式塗佈機、Hitachi AIC股份有限公司製真空疊合機等。 In the above lamination, when the lamella laminate has a protective thin In the case of the film, after the protective film is removed, the sheet-like laminate and the circuit board are preheated as necessary, and the sheet-like laminate is superposed on the circuit board while being pressed and heated. In the sheet-like laminate of the present invention, a method of laminating on a circuit substrate under reduced pressure by vacuum lamination is preferred. The conditions for the superposition are not particularly limited. For example, the pressure is reduced to 20 mmHg (26.7 hPa) or less for about 10 to 120 seconds, and then the pressing temperature (stacking temperature) is preferably set to 70 to 140 ° C, and the pressing pressure is applied. The (stacking pressure) is set to 0.1 to 1.5 MPa, preferably 0.5 to 1.2 MPa, and the pressing time (stacking time) is set to 5 to 180 seconds to perform lamination. In addition, the method of lamination may be batchwise or continuous depending on the roll. Vacuum lamination can be carried out using a commercially available vacuum laminator. For example, a Vacuum Applicator manufactured by Nichigo Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Nippon Seisakusho Co., Ltd., a roll dry coater manufactured by Hitachi Industries Co., Ltd., Hitachi, and the like. Vacuum laminating machine made by AIC Co., Ltd., etc.

然後在冷卻至室溫後，於剝離支撐體時，進行剝離並使樹脂組成物熱硬化而形成硬化物，藉此可將絕緣層形成 於電路基板上。熱硬化的條件，可因應樹脂組成物中之樹脂成分的種類、含量等來適當地選擇，例如在硬化溫度為100~220℃，佳為160~210℃，硬化時間為20分鐘~180分鐘，佳為30~120分鐘下加熱而進行。此外，亦可分成2階段來進行熱硬化。形成絕緣層後，於硬化前有未剝離支撐體時，亦可因應必要在此時剝離。 Then, after cooling to room temperature, when the support is peeled off, the resin composition is peeled off and the resin composition is thermally cured to form a cured product, whereby the insulating layer can be formed. On the circuit board. The conditions of the heat curing can be appropriately selected depending on the kind and content of the resin component in the resin composition, for example, the curing temperature is 100 to 220 ° C, preferably 160 to 210 ° C, and the hardening time is 20 minutes to 180 minutes. It is preferably heated for 30 to 120 minutes. In addition, it can be divided into two stages for thermal hardening. After the insulating layer is formed, when the support is not peeled off before the hardening, it may be peeled off at this time as necessary.

此外，亦可使用真空模壓機，將薄片狀層合 材料層合於電路基板的單面或雙面。於減壓下進行加壓及加熱之層合步驟，一般可使用真空熱模壓機來進行。例如可從支撐體側將加熱後之SUS板等的金屬板進行模壓來進行。模壓條件，係在70~250℃，佳為100~230℃的溫度下，且通常將減壓度設為0.01MPa以下，佳為0.001MPa以下的減壓下，將模壓壓力設為0.5~4MPa的範圍，模壓時間設為30~150分鐘之間來進行。加熱及加壓可在1階段中進行，但從控制樹脂的滲出之觀點來看，較佳係在2階段以上區分條件來進行。例如較佳係在溫度70~150℃、模壓壓力0.1~1.5MPa的範圍內進行第1階段的模壓，在溫度150~200℃、壓力0.5~4MPa的範圍內進行第2階段的模壓。各階段的時間，較佳是在20~120分鐘間進行。藉由使如此的樹脂組成物層熱硬化，可在電路基板上形成絕緣層。市售之真空熱模壓機，例如可列舉出MNPC-V-750-5-200(名機製作所股份有限公司製)、VH1-1603(北川精機股份有限公司製)等。 In addition, a laminar laminate can also be used using a vacuum molding machine. The material is laminated on one or both sides of the circuit substrate. The laminating step of pressurizing and heating under reduced pressure can generally be carried out using a vacuum hot press. For example, it can be performed by molding a metal plate such as a heated SUS plate from the side of the support. The molding conditions are 70 to 250 ° C, preferably 100 to 230 ° C, and the pressure is usually set to 0.01 MPa or less, preferably 0.001 MPa or less, and the molding pressure is set to 0.5 to 4 MPa. The range of the molding time is set to be between 30 and 150 minutes. The heating and the pressurization can be carried out in one stage, but from the viewpoint of controlling the bleeding of the resin, it is preferred to carry out the conditions in two or more stages. For example, it is preferable to carry out the first-stage molding at a temperature of 70 to 150 ° C and a molding pressure of 0.1 to 1.5 MPa, and to carry out the second-stage molding at a temperature of 150 to 200 ° C and a pressure of 0.5 to 4 MPa. The time of each stage is preferably carried out between 20 and 120 minutes. By thermally hardening such a resin composition layer, an insulating layer can be formed on the circuit board. For example, MNPC-V-750-5-200 (manufactured by Nago Seisakusho Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like are exemplified.

接著可對形成於電路基板上之絕緣層進行開 孔加工以形成導通孔、貫通孔。開孔加工，例如可藉由鑽孔、雷射、電漿等之一般所知的方法，且可因應必要組合此等方法來進行，最一般的方法為依據碳酸氣體雷射、YAG雷射等之雷射的開孔加工。於開孔加工前有未剝離支撐體時，可在此剝離。 Then, the insulating layer formed on the circuit substrate can be opened The holes are machined to form via holes and through holes. The hole drilling process can be carried out, for example, by a generally known method such as drilling, laser, plasma, etc., and can be performed by combining such methods as necessary. The most general method is based on a carbon dioxide gas laser, a YAG laser, or the like. Laser drilling. When there is an unstripped support before the drilling process, it can be peeled off here.

接著對絕緣層表面進行上述粗化處理，然後 藉由乾式電鍍或濕式電鍍於絕緣層上形成導體層。乾式電鍍，可使用蒸鍍、濺鍍、離子蒸鍍等之一般所知的方法來進行。濕式電鍍，可列舉出組合無電解電鍍與電解電鍍以形成導體層之方法、形成與導體層相反圖型之電鍍抗蝕層並僅藉由無電解電鍍來形成導體層之方法等。之後的圖型形成方法，例如可使用該業者所熟知的減成法、半加成法等，並藉由重複進行上述一連串的步驟，而成為層合有多段的增層之多層印刷配線板。本發明中，由於為低粗糙度及高撕離性，所以可適合地使用作為多層印刷配線板的增層。 Then, the surface of the insulating layer is subjected to the above roughening treatment, and then A conductor layer is formed on the insulating layer by dry plating or wet plating. Dry plating can be carried out by a generally known method such as vapor deposition, sputtering, or ion deposition. Examples of the wet plating include a method of forming electroless plating and electrolytic plating to form a conductor layer, a method of forming an electroplated resist layer having a pattern opposite to that of a conductor layer, and forming a conductor layer only by electroless plating. In the subsequent pattern forming method, for example, a subtractive method, a semi-additive method, or the like which is well known to those skilled in the art can be used, and by repeating the above-described series of steps, a multilayer printed wiring board in which a plurality of layers are laminated can be formed. In the present invention, since it is low in roughness and high in tearability, it is possible to suitably use a build-up layer as a multilayer printed wiring board.

[半導體裝置] [semiconductor device]

藉由使用上述方式製造出之多層印刷配線板，可製造半導體裝置。於本發明所能夠使用之多層印刷配線板的導通處構裝半導體晶片，可製造半導體裝置。所謂「導通處」，為「多層印刷配線板中傳遞電訊號之處」，該處可為表面或是被埋入之處之任一處皆可。此外，若為導通，則可為導體層的一部分或是除此之外的連接器等導電部 分。所謂「半導體晶片」，只要是以半導體為材料之電氣電路元件即可，並無特別限定。 A semiconductor device can be manufactured by using the multilayer printed wiring board manufactured in the above manner. A semiconductor device can be fabricated by arranging a semiconductor wafer at a conduction portion of a multilayer printed wiring board that can be used in the present invention. The so-called "conducting point" is "where the electrical signal is transmitted through the multilayer printed wiring board", which can be either the surface or the place where it is buried. In addition, if it is conductive, it may be a part of the conductor layer or a conductor such as a connector other than the conductor. Minute. The "semiconductor wafer" is not particularly limited as long as it is an electrical circuit element made of a semiconductor.

製造本發明之半導體裝置時之半導體晶片的 構裝方法，只要是可使半導體晶片有效地發揮功能者即可，並無特別限定，具體可列舉出打線接合構裝方法、覆晶構裝方法、無凸塊增層(BBUL)的構裝方法、異向性導電薄膜(ACF)的構裝方法、非導電性薄膜(NCF)的構裝方法等。 Semiconductor wafer when manufacturing the semiconductor device of the present invention The mounting method is not particularly limited as long as it can effectively function as a semiconductor wafer, and specifically, a wire bonding method, a flip chip mounting method, and a bumpless buildup (BBUL) package are exemplified. The method, the method of constructing an anisotropic conductive film (ACF), the method of constructing a non-conductive film (NCF), and the like.

[實施例] [Examples]

以下藉由實施例來具體地說明本發明，但本發明並不限定於此等實施例。以下的記載中，「份」在無特別言明時意味著「質量份」，「%」在無特別言明時意味著「質量%」。 Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited thereto. In the following description, "parts" means "parts by mass" unless otherwise stated, and "%" means "% by mass" unless otherwise stated.

〈測定方法及評估方法〉 <Measurement method and evaluation method>

首先說明各測定方法及評估方法。 First, each measurement method and evaluation method will be described.

[撕離強度、算術平均粗糙度(Ra)、均方根粗糙度(Rq)之測定用樣本的調製] [Modulation of sample for measurement of tear strength, arithmetic mean roughness (Ra), and root mean square roughness (Rq)] (1)層合板的底層處理 (1) Underlayer treatment of laminates

藉由MEC股份有限公司製CZ8100，將玻璃布基材環氧樹脂雙面覆銅層合板(銅箔厚度18μm、基板厚度0.3mm、松下電工股份有限公司製R5715ES)的雙面蝕刻 1μm來進行銅表面的粗化處理。 Double-sided etching of a glass cloth substrate epoxy double-sided copper clad laminate (copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Co., Ltd. R5715ES) by CZ8100 manufactured by MEC Co., Ltd. The copper surface was roughened by 1 μm.

(2)黏著薄膜的疊合 (2) Adhesion of adhesive film

使用分批式真空加壓疊合機(名機製作所股份有限公司製)MVLP-500，將實施例及比較例所製作之黏著薄膜，疊合於上述經粗化處理後之環氧樹脂雙面覆銅層合板的雙面。疊合，係減壓30秒並將氣壓設為13hPa以下，然後在100℃、壓力0.74MPa下壓著30秒來進行。 The adhesive film produced in the examples and the comparative examples was laminated on the double-sided epoxy resin after the roughening treatment using a batch vacuum pressure laminating machine (manufactured by Nago Seisakusho Co., Ltd.) MVLP-500. Both sides of the copper clad laminate. The lamination was carried out under reduced pressure for 30 seconds and the gas pressure was set to 13 hPa or less, and then pressed at 100 ° C under a pressure of 0.74 MPa for 30 seconds.

(3)樹脂組成物的硬化 (3) Hardening of the resin composition

從疊合後之黏著薄膜將作為支撐體的聚對苯二甲酸乙二酯(PET)薄膜剝離後，在100℃持續30分鐘且在180℃持續30分鐘之硬化條件下，使樹脂組成物硬化而形成絕緣層。 After peeling off the polyethylene terephthalate (PET) film as a support from the laminated adhesive film, the resin composition is hardened at 100 ° C for 30 minutes and at 180 ° C for 30 minutes under hardening conditions. An insulating layer is formed.

(4)粗化處理 (4) roughening treatment

將形成有絕緣層之層合板，於60℃中浸漬在作為膨潤液之Atotech Japan股份有限公司之含有二乙二醇單丁醚的Swelling Dip Securiganth P(二醇醚類、氫氧化鈉的水溶液)5分鐘(實施例1、比較例1、4、5)或是10分鐘(實施例2、3、比較例2、3、6)。接著於80℃中浸漬在作為粗化液之Atotech Japan股份有限公司的Concentrate Compact P(KMnO4：60g/L、NaOH：40g/L的水溶液)15分鐘(實施例1、比較例1、4、5)、20分 鐘(實施例2、3、比較例2、3、6)。最後，於40℃中浸漬在作為中和液之Atotech Japan股份有限公司的Reduction Solution Securiganth P(硫酸的水溶液)5分鐘。於80℃乾燥30分鐘後，將該基板作為評估基板A。 The laminate in which the insulating layer was formed was immersed in Swelling Dip Securiganth P (glycol ether, aqueous solution of sodium hydroxide) containing diethylene glycol monobutyl ether as a swelling liquid at 60 ° C in Atotech Japan Co., Ltd. 5 minutes (Example 1, Comparative Example 1, 4, 5) or 10 minutes (Examples 2, 3, Comparative Examples 2, 3, 6). Subsequently, it was immersed in Concentrate Compact P (KMnO 4 : 60 g/L, NaOH: 40 g/L aqueous solution) of Atotech Japan Co., Ltd. as a roughening liquid at 80 ° C for 15 minutes (Example 1, Comparative Examples 1, 4, 5), 20 minutes (Examples 2, 3, Comparative Examples 2, 3, 6). Finally, it was immersed in a reduction solution Securiganth P (aqueous solution of sulfuric acid) of Atotech Japan Co., Ltd. as a neutralizing liquid at 40 ° C for 5 minutes. After drying at 80 ° C for 30 minutes, the substrate was used as the evaluation substrate A.

(5)半加成工法的電鍍 (5) Electroplating of semi-additive method

對評估基板A進行電鍍而形成導體層。具體而言，於40℃將評估基板A浸漬於包含PdCl2之無電解電鍍用溶液5分鐘，接著於25℃浸潰於無電解電鍍用溶液20分鐘。於150℃加熱30分鐘進行回火處理後，形成抗蝕層，在藉由蝕刻形成圖型後，進行硫酸銅電解電鍍，以30μm的厚度形成導體層。接著於190℃進行60分鐘的回火處理。將該基板作為評估基板B。 The evaluation substrate A is plated to form a conductor layer. Specifically, the evaluation substrate A was immersed in a solution for electroless plating containing PdCl 2 at 40 ° C for 5 minutes, and then immersed in a solution for electroless plating at 25 ° C for 20 minutes. After heating at 150 ° C for 30 minutes and tempering, a resist layer was formed, and after patterning by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 μm. The tempering treatment was then carried out at 190 ° C for 60 minutes. This substrate was used as the evaluation substrate B.

[粗化後之算術平均粗糙度(Ra值)、均方根粗糙度(Rq值)的測定] [Measurement of arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) after roughening]

使用非接觸型表面粗糙度計(Veeco Instruments公司製WYKO NT3300)，藉由VSI Contact Mode、50倍的透鏡，將測定範圍設為121μm×92μm而對評估基板A進行測定，並從所得到之數值中求取Ra值、Rq值，並分別求取10點的平均值來測得。 Using a non-contact surface roughness meter (WYKO NT3300, manufactured by Veeco Instruments Co., Ltd.), the evaluation substrate A was measured by a VSI Contact Mode, a 50-fold lens, and the measurement range was 121 μm × 92 μm, and the obtained value was obtained. The Ra value and the Rq value were obtained and measured by taking an average value of 10 points.

[電鍍導體層之撕開強度(撕離強度)的測定] [Determination of tear strength (peeling strength) of electroplated conductor layer]

於評估基板B的導體層上，在寬10mm、長100mm 的部分上形成切口，剝離其一端並藉由夾持具(TSE股份有限公司、AUTO COM型試驗機AC-50C-SL)予以夾持，並測定於室溫(25℃)中以50mm/分的速度往垂直方向撕開35mm時之荷重(kgf/cm(N/cm))。 On the conductor layer of the evaluation substrate B, it is 10 mm wide and 100 mm long. A slit was formed in the portion, and one end thereof was peeled off and clamped by a holder (TSE Co., Ltd., AUTO COM type tester AC-50C-SL), and measured at room temperature (25 ° C) at 50 mm / min. The speed of the tear is 35 mm when it is torn in the vertical direction (kgf/cm (N/cm)).

[線熱膨脹係數(CTE)的測定] [Determination of linear thermal expansion coefficient (CTE)]

將實施例及比較例所製作之黏著薄膜，於200℃加熱90分鐘使其熱硬化，並從作為支撐體的PET薄膜剝離而藉此得到薄片狀的硬化物。將該硬化物切斷為寬5mm、長15mm、厚30mm的試驗片，並使用熱機械分析裝置Thermo Plus TMA8310(Rigaku股份有限公司製)，藉由拉伸加重法進行熱機械分析。在將試驗片裝著於前述裝置後，在荷重1g、升溫速度5℃/分的測定條件下連續測定2次。並算出於第2次的測定中從25℃至150℃為止之平均線熱膨脹係數(ppm)。 The adhesive film produced in the examples and the comparative examples was thermally cured at 200 ° C for 90 minutes, and peeled off from the PET film as a support to obtain a sheet-like cured product. The cured product was cut into a test piece having a width of 5 mm, a length of 15 mm, and a thickness of 30 mm, and subjected to thermomechanical analysis by a tensile weighting method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Co., Ltd.). After the test piece was placed in the above apparatus, the test piece was continuously measured twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5 ° C/min. The average linear thermal expansion coefficient (ppm) from 25 ° C to 150 ° C in the second measurement was calculated.

[破壞伸長度的測定] [Measurement of Destructive Elongation]

將實施例及比較例所製作之黏著薄膜，於200℃加熱90分鐘使其熱硬化，並將該硬化物裁切出啞鈴狀，剝離PET薄膜而得到試驗片。依據JIS K7127，使用Orientec公司製拉伸試驗機RTC-1250A對該試驗片進行拉伸強度測定，求取23℃時的破壞伸長度。 The adhesive film produced in the examples and the comparative examples was thermally cured at 200 ° C for 90 minutes, and the cured product was cut into a dumbbell shape, and the PET film was peeled off to obtain a test piece. The tensile strength of the test piece was measured using a tensile tester RTC-1250A manufactured by Orientec Co., Ltd. according to JIS K7127, and the breaking elongation at 23 ° C was determined.

<合成例1> <Synthesis Example 1> 具有雙二甲苯酚結構、雙酚芴結構之苯氧樹脂的合成 Synthesis of phenoxy resin with bisxylenol structure and bisphenol fluorene structure

將雙二甲苯酚型環氧樹脂(三菱化學股份有限公司製YX4000、環氧當量185)190g、雙酚芴(酚性羥基當量175)175g、環己酮150g裝入於反應容器，一邊攪拌一邊溶解。接著滴入氯化四甲基銨溶液0.5g，於氮氣氛圍中，於180℃反應5小時。反應結束後，使用濾布進行過濾並以溶劑來稀釋，藉此得到苯氧樹脂A。 190 g of bisxylenol type epoxy resin (YX4000, epoxy equivalent 185, manufactured by Mitsubishi Chemical Corporation), 175 g of bisphenol oxime (phenolic hydroxyl equivalent 175), and 150 g of cyclohexanone were placed in a reaction container while stirring. Dissolved. Then, 0.5 g of a tetramethylammonium chloride solution was added dropwise, and the mixture was reacted at 180 ° C for 5 hours in a nitrogen atmosphere. After completion of the reaction, filtration was carried out using a filter cloth and diluted with a solvent, whereby phenoxy resin A was obtained.

‧環氧當量：12200 ‧Epoxy equivalent: 12200

‧重量平均分子量：38000 ‧ Weight average molecular weight: 38000

‧為固體成分30質量%的MEK與環己酮之1：1溶液 ‧ is a solid solution of 30% by mass of a 1:1 solution of MEK and cyclohexanone

苯氧樹脂A具有下列結構。 The phenoxy resin A has the following structure.

<合成例2> <Synthesis Example 2> 具有雙二甲苯酚結構、雙酚苯乙酮結構、雙甲酚芴結構之苯氧樹脂的合成 Synthesis of phenoxy resin with bisxylenol structure, bisphenol acetophenone structure and biscresol oxime structure

將雙二甲苯酚型環氧樹脂(三菱化學股份有限公司製YX4000、環氧當量185)190g、雙酚苯乙酮(酚性羥基當量145)14g、雙甲酚芴(JFE Chemical股份有限公司製、酚性羥基當量190)170g、環己酮150g裝入於反應 容器，一邊攪拌一邊溶解。接著滴入氯化四甲基銨溶液0.5g，於氮氣氛圍中，於180℃反應5小時。反應結束後，使用濾布進行過濾並以溶劑來稀釋，藉此得到苯氧樹脂B。 190 g of bisxylenol type epoxy resin (YX4000 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), 14 g of bisphenol acetophenone (phenolic hydroxyl equivalent 145), and biscresol oxime (manufactured by JFE Chemical Co., Ltd.) , phenolic hydroxyl equivalent 190) 170g, cyclohexanone 150g charged in the reaction The container was dissolved while stirring. Then, 0.5 g of a tetramethylammonium chloride solution was added dropwise, and the mixture was reacted at 180 ° C for 5 hours in a nitrogen atmosphere. After completion of the reaction, filtration was carried out using a filter cloth and diluted with a solvent, whereby phenoxy resin B was obtained.

‧環氧當量：11000 ‧Epoxy equivalent: 11000

‧重量平均分子量：36000 ‧ Weight average molecular weight: 36000

‧固體成分30質量%的MEK與環己酮之1：1溶液 ‧ Solid solution 30% by mass of 1:1 solution of MEK and cyclohexanone

尚且，苯氧樹脂B具有下列結構。 Further, the phenoxy resin B has the following structure.

<合成例3> <Synthesis Example 3> 具有雙二甲苯酚結構、雙酚苯乙酮結構之苯氧樹脂的合成 Synthesis of phenoxy resin with bisxylenol structure and bisphenol acetophenone structure

將雙二甲苯酚型環氧樹脂(三菱化學股份有限公司製YX4000、環氧當量185)100g、雙酚苯乙酮80g、及環己酮150g裝入於反應容器，一邊攪拌一邊溶解。接著滴入氯化四甲基銨溶液0.5g，於氮氣氛圍中，於180℃反應5小時。反應結束後，使用濾布進行過濾並以溶劑來稀釋， 藉此得到苯氧樹脂C。苯氧樹脂C，由於不具有芴結構，故成為本發明之參考例。 100 g of bis xylenol type epoxy resin (YX4000 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 185), 80 g of bisphenol acetophenone, and 150 g of cyclohexanone were placed in a reaction container, and dissolved while stirring. Then, 0.5 g of a tetramethylammonium chloride solution was added dropwise, and the mixture was reacted at 180 ° C for 5 hours in a nitrogen atmosphere. After the reaction is completed, it is filtered using a filter cloth and diluted with a solvent. Thereby, a phenoxy resin C was obtained. The phenoxy resin C is a reference example of the present invention because it does not have a fluorene structure.

‧環氧當量：13000 ‧Epoxy equivalent: 13000

‧重量平均分子量：38000 ‧ Weight average molecular weight: 38000

‧固體成分30質量%的MEK與環己酮之1：1溶液 ‧ Solid solution 30% by mass of 1:1 solution of MEK and cyclohexanone

苯氧樹脂C具有下列結構。 The phenoxy resin C has the following structure.

<實施例1> <Example 1>

將雙酚型環氧樹脂(新日鐵化學股份有限公司製「ZX1059」、雙酚A型與雙酚F型的1：1混合品、環氧當量169)10份、結晶性二官能環氧樹脂(三菱化學股份有限公司製「YX4000HK」、環氧當量約185)10份、二環戊二烯型環氧樹脂(DIC股份有限公司製「HP-7200H」、環氧當量275)20份投入於溶劑油35份，一邊攪拌一邊加熱溶解。冷卻至室溫後，將苯氧樹脂A的12份、含三嗪骨架酚系硬化劑(DIC股份有限公司製「LA-7054」之環氧當量125之固體成分60%的MEK溶液)12份、萘型硬化劑(新日鐵化學股份有限公司製「SN-485」之羥基當量215之固體成分60%的MEK溶液)15份、硬化促進劑(4-二甲基胺基吡啶(DMAP)、固體成分2質量%的MEK溶液)3份、難燃劑(三光股份有限公司製「HCA- HQ」、10-(2,5-二羥苯基)-10-氫-9-噁-10-膦菲-10-氧化物、平均粒徑2μm)2份、以苯基胺基矽烷系偶合劑(信越化學股份有限公司製「KBM573」)進行表面處理之球形二氧化矽(平均粒徑0.24μm、Admatechs股份有限公司製「SOC1」、每單位面積的碳量0.36mg/m2)150份混合於此，藉由高速旋轉混合機均一地分散，而製作出樹脂清漆。接著於經進行脫模處理後之聚對苯二甲酸乙二酯薄膜(Lintec股份有限公司製「AL5」、厚度38μm、以及線熱膨脹係數(CTE)、及破壞伸長度的測定用硬化物製作時之「PET501010」、厚度50μm)的脫模面上，以使乾燥後之樹脂組成物層的厚度成為30μm之方式均一地塗佈樹脂清漆，於80~120℃(平均100℃)乾燥4分鐘而製作出黏著薄膜。 Bisphenol type epoxy resin (ZX1059, manufactured by Nippon Steel Chemical Co., Ltd., 1:1 mixture of bisphenol A and bisphenol F, epoxide equivalent 169), 10 parts, crystalline difunctional epoxy 20 parts of resin ("XX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 185), 20 parts of dicyclopentadiene type epoxy resin ("HP-7200H" manufactured by DIC Co., Ltd., epoxy equivalent 275) 35 parts of solvent oil was heated and dissolved while stirring. After cooling to room temperature, 12 parts of phenoxy resin A and a triazine-based phenolic curing agent (MEK solution of 60% solid content of epoxide equivalent 125 of "LA-7054" manufactured by DIC Corporation) were used. Naphthalene type hardener (MEK solution of 60% solid content of hydroxyl equivalent of 215 of "SN-485" manufactured by Nippon Steel Chemical Co., Ltd.) 15 parts, hardening accelerator (4-dimethylaminopyridine (DMAP)) 3 parts by mass of MEK solution of solid content), flame retardant (HCA-HQ, manufactured by Sanko Co., Ltd., 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-ox-10 -2 bisphosphonium oxide, 2 μm of an average particle diameter of 2 μm, and spherical cerium oxide (average particle diameter 0.24) surface-treated with a phenylamino decane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) Μm, "SOC1" manufactured by Admatech Co., Ltd., and a carbon content of 0.36 mg/m 2 per unit area) were mixed here, and were uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish. Then, after the polyethylene terephthalate film ("AL5" manufactured by Lintec Co., Ltd., thickness 38 μm, linear thermal expansion coefficient (CTE), and cured product for measuring elongation at break) after the release treatment was produced, The resin varnish was uniformly applied to the release surface of the "PET501010" and the thickness of 50 μm so that the thickness of the resin composition layer after drying was 30 μm, and dried at 80 to 120 ° C (average 100 ° C) for 4 minutes. Make an adhesive film.

<實施例2> <Example 2>

將液狀萘型環氧樹脂(環氧當量144、DIC股份有限公司製「HP4032SS」)5份、結晶性二官能環氧樹脂(三菱化學股份有限公司製「YX4000HK」、環氧當量約185)5份、聯苯型環氧樹脂(日本化藥股份有限公司製「NC3000L」、環氧當量269)12份投入於溶劑油30份，一邊攪拌一邊加熱溶解。冷卻至室溫後，將苯氧樹脂A的5份、雙酚A二氰酸酯的預聚物(Lonza Japan股份有限公司製「BA230S75」、氰酸酯當量約232、非揮發份75質量%的MEK溶液)20份、酚-酚醛型多官能氰酸酯 樹脂(Lonza Japan股份有限公司製「PT30S」、氰酸酯當量約133、非揮發份85質量%的MEK溶液)6份、硬化促進劑(4-二甲基胺基吡啶、固體成分2質量%的MEK溶液)1份、硬化促進劑(東京化成股份有限公司製、鈷(III)乙醯丙酮酸(Co(III)Ac)、固體成分1質量%的MEK溶液)3份、橡膠粒子(Ganz Chemical股份有限公司製、Stafyroid AC3816N)2份、難燃劑(三光股份有限公司製「HCA-HQ」、10-(2,5-二羥苯基)-10-氫-9-噁-10-膦菲-10-氧化物、平均粒徑2μm)2份、以苯基胺基矽烷系偶合劑(信越化學股份有限公司製「KBM573」)進行表面處理之球形二氧化矽(平均粒徑0.5μm、Admatechs股份有限公司製「SOC2」、每單位面積的碳量0.39mg/m2)100份混合於此，藉由高速旋轉混合機均一地分散，而製作出樹脂清漆。接著與實施例1相同地製作出黏著薄膜。 5 parts of a liquid naphthalene type epoxy resin (epoxy equivalent 144, "HP4032SS" manufactured by DIC Co., Ltd.), a crystalline difunctional epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, and an epoxy equivalent of about 185) 12 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 269) was added to 30 parts of solvent oil, and heated and dissolved while stirring. After cooling to room temperature, 5 parts of phenoxy resin A and a prepolymer of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan Co., Ltd., cyanate equivalent: about 232, and nonvolatile content of 75 mass%) 20 parts, phenol-phenolic type polyfunctional cyanate resin ("PT30S" manufactured by Lonza Japan Co., Ltd., phthalate equivalent: 133, non-volatile 85 mass% MEK solution) 6 parts, hardening promotion 1 part of a solvent (4-dimethylaminopyridine, a solid content of 2% by mass of MEK solution), a hardening accelerator (manufactured by Tokyo Chemical Industry Co., Ltd., cobalt (III) acetoacetate (Co(III)Ac), 3 parts of a solid content of 1% by mass of MEK solution, 2 parts of rubber particles (manufactured by Ganz Chemical Co., Ltd., Stafyroid AC3816N), and a flame retardant (HCA-HQ, manufactured by Sanko Co., Ltd., 10-(2,5-) Dihydroxyphenyl)-10-hydrogen-9-oxo-10-phosphaphenanthrene-10-oxide, 2 μm of average particle size 2 parts, phenylamino decane coupling agent (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) </ RTI> 100 parts of spherical cerium oxide (average particle size: 0.5 μm, "SOC2" manufactured by Admatech Co., Ltd., carbon content per unit area: 0.39 mg/m 2 ) Thus, a resin varnish was produced by uniformly dispersing by a high-speed rotary mixer. Then, an adhesive film was produced in the same manner as in Example 1.

<實施例3> <Example 3>

將雙酚型環氧樹脂(新日鐵化學股份有限公司製「ZX1059」、雙酚A型與雙酚F型的1：1混合品、環氧當量169)10份、聯苯型環氧樹脂(日本化藥股份有限公司製「NC3000L」、環氧當量269)12份投入於溶劑油30份，一邊攪拌一邊加熱溶解。冷卻至室溫後，將苯氧樹脂B的17份、活性酯樹脂(DIC股份有限公司製「HPC8000-65T」、重量平均分子量約2700、活性基當量 約223之非揮發份65質量%的甲苯溶液)34份、硬化促進劑(4-二甲基胺基吡啶、固體成分2質量%的MEK溶液)6份、難燃劑(三光股份有限公司製「HCA-HQ」、10-(2,5-二羥苯基)-10-氫-9-噁-10-膦菲-10-氧化物、平均粒徑2μm)2份、以苯基胺基矽烷系偶合劑(信越化學股份有限公司製「KBM573」)進行表面處理之球形二氧化矽(平均粒徑0.5μm、Admatechs股份有限公司製「SOC2」、每單位面積的碳量0.39mg/m2)15份混合於此，藉由高速旋轉混合機均一地分散，而製作出樹脂清漆。接著與實施例1相同地製作出黏著薄膜。 Bisphenol type epoxy resin (ZX1059 made by Nippon Steel Chemical Co., Ltd., 1:1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 10 parts, biphenyl type epoxy resin (Noked Chemical Co., Ltd. "NC3000L", epoxy equivalent 269) 12 parts were put into 30 parts of solvent oil, and heated and dissolved while stirring. After cooling to room temperature, 17 parts of phenoxy resin B, an active ester resin ("HPC8000-65T" manufactured by DIC Corporation, a weight average molecular weight of about 2700, an active group equivalent of about 223, and a nonvolatile content of 65 mass% of toluene). 34 parts of solution, 6 parts of hardening accelerator (4-dimethylaminopyridine, MEK solution of solid content 2% by mass), flame retardant (HCA-HQ, manufactured by Sanko Co., Ltd., 10-(2, 5-dihydroxyphenyl)-10-hydrogen-9-oxo-10-phosphanthene-10-oxide, average particle size 2 μm) 2 parts, phenylamino decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) "KBM573") 15 parts of spherical cerium oxide (average particle diameter: 0.5 μm, "SOC2" manufactured by Admatech Co., Ltd., and carbon content per unit area of 0.39 mg/m 2 ) were mixed here, and rotated by high speed. The mixer was uniformly dispersed to produce a resin varnish. Then, an adhesive film was produced in the same manner as in Example 1.

<比較例1> <Comparative Example 1>

除了將實施例1之苯氧樹脂A的12份變更為雙酚A型苯氧樹脂(三菱化學股份有限公司製「E1256B40」、固體成分40質量%的MEK溶液、環氧當量8000、重量平均分子量約50000)10份之外，其他與實施例1完全相同而製作出黏著薄膜。 In addition, 12 parts of the phenoxy resin A of the first embodiment was changed to a bisphenol A type phenoxy resin ("E1256B40" manufactured by Mitsubishi Chemical Corporation, a MEK solution having a solid content of 40% by mass, an epoxy equivalent of 8000, and a weight average molecular weight. An adhesive film was produced in the same manner as in Example 1 except for about 50,000).

<比較例2> <Comparative Example 2>

除了將實施例2之苯氧樹脂A的5份變更為合成例3之苯氧樹脂C的5份之外，其他與實施例2完全相同而製作出黏著薄膜。 An adhesive film was produced in the same manner as in Example 2 except that 5 parts of the phenoxy resin A of Example 2 was changed to 5 parts of the phenoxy resin C of Synthesis Example 3.

<比較例3> <Comparative Example 3>

除了將實施例3之苯氧樹脂B的17份變更為合成例3之苯氧樹脂C的17份之外，其他與實施例3完全相同而製作出黏著薄膜。 An adhesive film was produced in the same manner as in Example 3 except that 17 parts of the phenoxy resin B of Example 3 was changed to 17 parts of the phenoxy resin C of Synthesis Example 3.

<比較例4> <Comparative Example 4>

除了將實施例1之苯氧樹脂12份變更為雙酚A型環氧樹脂(三菱化學股份有限公司製「jER1009」、環氧當量2740、固體成分40質量%的MEK與環己酮之1：1溶液)10份之外，其他與實施例1完全相同而製作出黏著薄膜。 In addition, 12 parts of the phenoxy resin of Example 1 was changed to bisphenol A type epoxy resin ("JER1009" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 2740, 40% by mass of MEK and cyclohexanone 1: An adhesive film was produced in the same manner as in Example 1 except that the solution was 10 parts.

<比較例5> <Comparative Example 5>

除了將實施例1之苯氧樹脂A的添加量從12份變更為50份之外，其他與實施例1完全相同而製作出黏著薄膜。 An adhesive film was produced in the same manner as in Example 1 except that the amount of the phenoxy resin A of Example 1 was changed from 12 parts to 50 parts.

<比較例6> <Comparative Example 6>

除了將實施例1之苯氧樹脂A的含三嗪骨架酚系硬化劑(DIC股份有限公司製「LA-7054」之環氧當量125之固體成分60%的MEK溶液)12份、及萘型硬化劑(新日鐵化學股份有限公司製「SN-485」之羥基當量215之固體成分60%的MEK溶液)15份，變更為硬化劑(二氰二醯胺、三菱化學股份有限公司製「DICY7」)3份之外，其他與實施例1完全相同而製作出黏著薄膜。由於上述 DICY7為二氰二醯胺，故均不屬於酚硬化劑、氰酸酯硬化劑、活性酯硬化劑中的任1種。 In addition to the triazine-based phenolic curing agent of the phenoxy resin A of Example 1, a MEK solution of 60% solid content of an epoxy equivalent of 125% of "LA-7054" manufactured by DIC Corporation, and a naphthalene type. 15 parts of a hardener (MEK solution of 60% solid content of hydroxy group equivalent 215 of "SN-485" manufactured by Nippon Steel Chemical Co., Ltd.) was changed to a curing agent (manufactured by Mitsubishi Chemical Corporation) An adhesive film was produced in the same manner as in Example 1 except for three parts of DICY7"). Due to the above Since DICY7 is dicyandiamide, it is not one of a phenol hardener, a cyanate hardener, and an active ester hardener.

結果如第1表及第2表所示。 The results are shown in Tables 1 and 2.

從第1表及第2表的結果中，可得知使用本 申請案發明之硬化性樹脂組成物之實施例1~3中，具有低粗糙度、充分的撕離強度。低線熱膨脹係數、及充分的破壞伸長度。另一方面，比較例1~6中，由於未使用本申請案發明之硬化性樹脂組成物，所以算術平均粗糙度、均方根粗糙度大，撕離強度小，且線熱膨脹係數亦大。 From the results of the first and second tables, the use of the book can be known. In Examples 1 to 3 of the curable resin composition of the invention of the present application, it has low roughness and sufficient tear strength. Low line thermal expansion coefficient and sufficient breaking elongation. On the other hand, in Comparative Examples 1 to 6, since the curable resin composition of the invention of the present application was not used, the arithmetic mean roughness and the root mean square roughness were large, the tear strength was small, and the linear thermal expansion coefficient was also large.

Claims (15)

一種硬化性樹脂組成物，其係含有：(A)具有茀結構之苯氧樹脂、(B)環氧樹脂、及(C)硬化劑之樹脂組成物，其特徵為：(C)硬化劑包含選自酚硬化劑、氰酸酯硬化劑、活性酯硬化劑之1種以上，且前述(A)苯氧樹脂與前述(B)環氧樹脂與前述(C)硬化劑之合計為100質量%時，前述(A)苯氧樹脂為1~20質量%。 A curable resin composition comprising: (A) a phenoxy resin having a fluorene structure, (B) an epoxy resin, and (C) a resin composition of a curing agent, characterized in that: (C) a curing agent comprises One or more selected from the group consisting of a phenol curing agent, a cyanate curing agent, and an active ester curing agent, and the total of the (A) phenoxy resin and the (B) epoxy resin and the (C) curing agent are 100% by mass. In the case of the above (A) phenoxy resin, it is 1 to 20% by mass. 如申請專利範圍第1項之硬化性樹脂組成物，其中前述(A)苯氧樹脂的重量平均分子量為8000~100000。 The curable resin composition of claim 1, wherein the (A) phenoxy resin has a weight average molecular weight of 8,000 to 100,000. 如申請專利範圍第1或2項之硬化性樹脂組成物，其中前述(A)苯氧樹脂具有無取代雙酚茀結構或雙甲酚茀結構。 The curable resin composition according to claim 1 or 2, wherein the (A) phenoxy resin has an unsubstituted bisphenol fluorene structure or a biscresol oxime structure. 如申請專利範圍第1或2項之硬化性樹脂組成物，其中前述(B)環氧樹脂選自由雙酚型環氧樹脂、結晶性二官能環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂及此等環氧樹脂的混合物所組成之群組。 The curable resin composition according to claim 1 or 2, wherein the (B) epoxy resin is selected from the group consisting of a bisphenol type epoxy resin, a crystalline difunctional epoxy resin, and a dicyclopentadiene type epoxy resin. A group consisting of a naphthalene type epoxy resin, a biphenyl type epoxy resin, and a mixture of such epoxy resins. 如申請專利範圍第1或2項之硬化性樹脂組成物，其中前述硬化性樹脂組成物中的非揮發成分為100質量%時，前述(A)苯氧樹脂的含量為0.3~10質量%，前述(B)環氧樹脂的含量為5~30質量%，前述(C)硬化 劑的含量為3~20質量%。 The curable resin composition of the first or second aspect of the invention, wherein the content of the (A) phenoxy resin is from 0.3 to 10% by mass, wherein the non-volatile component in the curable resin composition is 100% by mass, The content of the above (B) epoxy resin is 5 to 30% by mass, and the aforementioned (C) hardening The content of the agent is 3 to 20% by mass. 如申請專利範圍第1或2項之硬化性樹脂組成物，其中進一步含有(D)無機填料。 The curable resin composition of claim 1 or 2, further comprising (D) an inorganic filler. 如申請專利範圍第6項之硬化性樹脂組成物，其中前述(D)無機填料的平均粒徑為0.01~5μm。 The curable resin composition of claim 6, wherein the (D) inorganic filler has an average particle diameter of 0.01 to 5 μm. 如申請專利範圍第6項之硬化性樹脂組成物，其中前述硬化性樹脂組成物中的非揮發成分為100質量%時之前述(D)無機填料的含量為30~90質量%。 The curable resin composition according to claim 6, wherein the content of the (D) inorganic filler in the non-volatile component in the curable resin composition is 100% by mass to 90% by mass. 如申請專利範圍第6項之硬化性樹脂組成物，其中前述(D)無機填料為二氧化矽。 The curable resin composition of claim 6, wherein the (D) inorganic filler is cerium oxide. 一種多層印刷配線板之絕緣層用硬化性樹脂組成物，其特徵係含有如申請專利範圍第1或2項之硬化性樹脂組成物。 A curable resin composition for an insulating layer of a multilayer printed wiring board, characterized by comprising a curable resin composition according to claim 1 or 2. 一種多層印刷配線板之增層用硬化性樹脂組成物，其特徵係含有如申請專利範圍第1或2項之硬化性樹脂組成物。 A curable resin composition for a build-up layer of a multilayer printed wiring board, characterized by comprising a curable resin composition according to claim 1 or 2. 一種薄片狀層合材料，其特徵係含有如申請專利範圍第1或2項之硬化性樹脂組成物。 A sheet-like laminate comprising a curable resin composition as claimed in claim 1 or 2. 一種多層印刷配線板，其特徵係包含使如申請專利範圍第1或2項之硬化性樹脂組成物熱硬化而得到之絕緣層。 A multilayer printed wiring board characterized by comprising an insulating layer obtained by thermally curing a curable resin composition according to claim 1 or 2. 一種多層印刷配線板，其特徵係包含使如申請專利範圍第12項之薄片狀層合材料熱硬化而得到之絕緣層。 A multilayer printed wiring board characterized by comprising an insulating layer obtained by thermally hardening a sheet-like laminate according to claim 12 of the patent application. 一種半導體裝置，其特徵係包含如申請專利範圍第14項之多層印刷配線板。 A semiconductor device characterized by comprising the multilayer printed wiring board of claim 14 of the patent application.
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