TW200923007A - Epoxy resin composition - Google Patents

Epoxy resin composition Download PDF

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Publication number
TW200923007A
TW200923007A TW097136127A TW97136127A TW200923007A TW 200923007 A TW200923007 A TW 200923007A TW 097136127 A TW097136127 A TW 097136127A TW 97136127 A TW97136127 A TW 97136127A TW 200923007 A TW200923007 A TW 200923007A
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Taiwan
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epoxy resin
resin composition
insulating layer
layer
epoxy
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TW097136127A
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Chinese (zh)
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TWI433887B (en
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Shigeo Nakamura
Kenji Kawai
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Ajinomoto Kk
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Publication of TWI433887B publication Critical patent/TWI433887B/en

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    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
    • H05K3/387—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive for electroless plating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4661—Adding a circuit layer by direct wet plating, e.g. electroless plating; insulating materials adapted therefor

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Epoxy Resins (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

Disclosed is an epoxy resin composition suitable for an insulating layer of a multilayer printed wiring board. This epoxy resin composition enables to obtain an insulating layer with excellent flame retardance, which insulating layer has a roughened surface exhibiting high adhesion to a plated conductor even though the roughness degree of the roughened surface after roughening treatment is relatively low. Specifically disclosed is an epoxy resin composition characterized by containing (A) an epoxy resin, (B) an epoxy curing agent, (C) a phenoxy resin and/or a polyvinyl acetal resin, and (D) a phosphorus-containing benzoxazine compound.

Description

200923007 九、發明說明 【發明所屬之技術領域】 本發明係有關適用於形成多層印刷電路板之絕緣層之 環氧樹脂組成物。 【先前技術】 近幾年來，隨著電子機器的小型化、高性能化發展， 多層印刷電路板亦更進一步進展至多層化或、配線之微細 化以及高密度化。至於適用於形成高·密度微細配線之導體 形成方法，已知有將絕緣層表面進行粗糙化處理後，以無 電解電鍍形成導體層之加成法（additive method )，以及 以無電解電鍍及電解電鍍形成導體層之半加成法（semi_ additive method)。該等方法中，主要係藉由粗糙化處理 所形成之絕緣層表面的凹凸而確保絕緣層與電鍍導體層間 之密著性。亦即，以絕緣層表面具有凹凸而獲得與電鍍層 間之錨定效果。因此，爲使密著性增高，考慮有更增大絕 緣層表面的凹凸程度（粗糙度）。 然而’爲使配線益發高密度化絕緣層表面之粗糙度較 好較小。亦即，藉由無電解電鍍、電解電鑛形成導體層後 ’藉由快速蝕刻（flash etching )去除薄膜之電鍍層而完 成配線之際，若絕緣層表面之粗糙度大，則爲了去除潛埋 在凹部之導體層而必要長時間進行快速蝕刻，若長時間進 行快速蝕刻’將受其影響而損傷微細配線或使其斷線之危 險性高。因此，爲了形成高信賴性之高密度配線，而要求 -4 - 200923007 即使於絕緣層表面進行粗糙化處理後之粗糙度小，其與電 鍍導體間之密著性仍需優異。 再者，多層印刷基板之絕緣材必須具有難燃性，尤其 近幾年，由對環境方面之考慮，傾向於使用非鹵系之難燃 劑。作爲非鹵系難燃劑之例，已知有磷系難燃劑，例如於 特開200 1 - 1 8 1 3 75號公報中，揭示有含有含磷環氧樹脂及 酚系硬化劑、特定之苯氧基樹脂等之環氧樹脂組成物，於 使用在多層印刷電路板之絕緣層時，其耐熱性、難燃性高 ，由電鍍形成之導體層之剝離強度優異。然而，該專利說 明書之實施例中記載之粗糙化後絕緣層表面之粗糙度大， 於微細配線化有其界限。 又例如於特開2003- 1 1 269號公報中，揭示含有具有 酚性羥基之磷化合物之環氧樹脂組成物於使用作爲貼附銅 箔絕緣材時，其絕緣性、耐熱性優異。然而，此專利文獻 中，並未揭示於作爲絕緣層使用時，可獲得低粗糙度且高 剝離強度之樹脂組成物，且亦未提示此等問題。 【發明內容】 [本發明欲解決之課題] 本發明係鑑於上述情事而完成者，解決此之課題係提 供一種環氧樹脂組成物，其係適合使用作爲多層印刷電路 板之絕緣層之環氧樹脂組成物，其可達成儘管粗糙化處理 後之粗糙化面之粗糙度比較小，但該粗糙化面對於電鍍導 體仍顯示高的密著力且可難燃性優異之絕緣層。 -5- 200923007 [用以解決課題之手段] 本發明人欲解決上述課題而積極硏究之結果，發現對 於環氧樹脂、環氧硬化劑以及苯氧基樹脂及/或聚乙烯縮 醛樹脂與含磷之苯并噁嗪化合物所調配之環氧樹脂組成物 ，使該環氧樹脂硬化所得之硬化物若經粗糙化處理，即使 所得之粗糙化面粗糙度比較小亦可以高的密著力與電鍍導 體進行密著，且具有優異難燃性，因而完成本發明。 亦即，本發明包含下述內容。 Π]—種環氧樹脂組成物，其特徵爲含有（A)環氧樹 脂、（B)環氧硬化劑、（C)苯氧樹脂及/或聚乙烯縮醛 樹脂以及（D)含有磷之苯并噁嗪化合物。 [2]如上述[1 ]記載之環氧樹脂組成物，其中該含磷之 苯并噁嗪化合物爲以下式（1)表示之含磷苯并噁嗪化合 物： [化1]BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition suitable for forming an insulating layer of a multilayer printed circuit board. [Prior Art] In recent years, with the development of miniaturization and high performance of electronic devices, multilayer printed circuit boards have further progressed to multilayering, miniaturization of wiring, and high density. As for a method of forming a conductor suitable for forming a high-density fine wiring, an additive method of forming a conductor layer by electroless plating after roughening the surface of the insulating layer, and electroless plating and electrolysis are known. Electroplating forms a semi-additive method of the conductor layer. In these methods, the adhesion between the insulating layer and the plated conductor layer is mainly ensured by the unevenness of the surface of the insulating layer formed by the roughening treatment. Namely, the anchoring effect with the plating layer is obtained by having irregularities on the surface of the insulating layer. Therefore, in order to increase the adhesion, it is considered to increase the degree of roughness (roughness) of the surface of the insulating layer. However, the roughness of the surface of the insulating layer is preferably small in order to make the wiring high. That is, after the conductor layer is formed by electroless plating or electrolytic electrowinning, the wiring is removed by flash etching to remove the plating layer of the film. If the surface roughness of the insulating layer is large, the buried layer is removed. It is necessary to perform rapid etching for a long time in the conductor layer of the concave portion, and if the rapid etching is performed for a long time, the risk of damaging the fine wiring or breaking the wire is high. Therefore, in order to form high-reliability high-density wiring, it is required that -4 - 200923007, even if the roughness of the surface of the insulating layer is roughened, the adhesion to the electroplated conductor is required to be excellent. Further, the insulating material of the multilayer printed substrate must be flame retardant, and in recent years, it has been apt to use a non-halogen-based flame retardant from the viewpoint of the environment. As an example of a non-halogen-based flame retardant, a phosphorus-based flame retardant is known. For example, JP-A-200 1 - 1 8 1 3 75 discloses that a phosphorus-containing epoxy resin and a phenolic curing agent are contained, and specific When an epoxy resin composition such as a phenoxy resin is used as an insulating layer of a multilayer printed wiring board, heat resistance and flame retardancy are high, and the peeling strength of the conductor layer formed by plating is excellent. However, the roughness of the surface of the insulating layer after roughening described in the examples of the patent specification is large, and there is a limit to fine wiring. In the case of using an epoxy resin composition containing a phosphorus compound having a phenolic hydroxyl group as an attached copper foil insulating material, it is excellent in insulation property and heat resistance. However, this patent document does not disclose a resin composition which can obtain low roughness and high peel strength when used as an insulating layer, and does not suggest such a problem. [Problem to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an epoxy resin composition which is suitable for use as an epoxy layer of an insulating layer of a multilayer printed circuit board. In the resin composition, although the roughness of the roughened surface after the roughening treatment is relatively small, the roughened surface exhibits a high adhesion to the plated conductor and is excellent in flame retardancy. -5-200923007 [Means for Solving the Problem] The inventors of the present invention have found that epoxy resin, epoxy hardener, phenoxy resin and/or polyvinyl acetal resin and the like have been actively studied. The epoxy resin composition prepared by the phosphorus-containing benzoxazine compound, if the cured product obtained by curing the epoxy resin is roughened, the adhesion of the roughened surface is relatively small, and the adhesion can be high. The plated conductor is adhered and has excellent flame retardancy, and thus the present invention has been completed. That is, the present invention encompasses the following.环氧树脂] - an epoxy resin composition characterized by containing (A) an epoxy resin, (B) an epoxy hardener, (C) a phenoxy resin and/or a polyvinyl acetal resin, and (D) a phosphorus-containing compound Benzooxazine compounds. [2] The epoxy resin composition according to the above [1], wherein the phosphorus-containing benzoxazine compound is a phosphorus-containing benzoxazine compound represented by the following formula (1): [Chemical Formula 1]

[3 ]如上述[1 ]或[2 ]記載之環氧樹脂組成物，其中該環 氧硬化劑爲選自酚系硬化劑、萘酚系硬化劑及活性酯系硬 化劑之1種以上之環氧硬化劑。 [4]如上述[1]至[3]中任一項記載之環氧樹脂組成物， 200923007 其中以該環氧樹脂組成物之不揮發成分作爲1 〇〇質量％時 ，成分（A)之含量爲10〜5 0質量％，成分（C)之含量爲 2〜20質量％，以及成分（D)之含量爲2〜20質量％，且環 氧硬化劑之反應基相對於環氧樹脂組成物中存在之1個環 氧基之比例爲1: 0.5〜1: 1.1。 [5 ]如上述[1 ]至[4 ]中任一項記載之環氧樹脂組成物， 其進而含有無機塡充劑。 [6 ]如上述[5 ]記載之環氧樹脂組成物，其中以該環氧 樹脂組成物之不揮發成分作爲1〇〇質量％時，該無機塡充 劑之含量爲10〜60質量％。 [7] —種接著薄膜，其特徵係於支撐薄膜上形成有上述 [1]至[6]中任一項記載之環氧樹脂組成物之層而成者。 [8] —種預浸片，其特徵係於由纖維所構成薄片狀纖維 基材中含浸有上述[1 ]至[6]中任一項記載之環氧樹脂組成 物而成者。 [9] 一種多層印刷電路板，其特徵係形成有由上述[1 ] 至[6]中任一項記載之環氧樹脂組成物的硬化物所成之絕緣 層者。 [10] —種多層印刷電路板之製造方法，其具有在內層 電路基板上形成絕緣層之步驟以及在該絕緣層上形成導體 層之步驟者，其特徵爲該絕緣層係使上述[1]至[6]中任一 項記載之環氧樹脂組成物加以熱硬化所形成，該導體層係 藉由於該絕緣層表面經粗糙化處理之粗糙化面上進行電鍍 而形成。 -7- 200923007 [11] 一種多層印刷電路板之製造方法，其具有在內層 電路基板上形成絕緣層之步驟以及在該絕緣層上形成導體 層之步驟者’其特徵爲具有絕緣層形成步驟、該絕緣層之 粗面化步驟及對該粗面進行電鍍之步驟；該絕緣層形成步 驟係具有於內層電路基板上層合上述[7]記載之支持薄膜上 之形成層之接著薄膜之步驟以及使環氧樹脂組成物熱硬化 之步驟。 [1 2] —種多層印刷電路板之製造方法，其具有在內層 電路基板上形成絕緣層之步驟以及在該絕緣層上形成導體 層之步驟者，其特徵爲該絕緣層係在內層電路基板上層合 上述[8 ]記載之預浸片，使環氧樹脂組成物加以熱硬化所形 成’該導體層係藉由於該絕緣層表面經粗糙化處理之粗糙 化面上進行電鍍而形成。 [13]如上述[10]至[12]中任一項記載之多層印刷電路 板之製造方法，其中該粗糙化處理係使用鹼性過錳酸溶液 而進行。 [發明效果] 依據本發明，可於多層印刷電路板中導入即使粗糙化 處理後之粗糙化面粗糙度比較小其與藉電鍍形成之導體層 亦具有優異之密著強度且具有優異難燃性之絕緣層。 【實施方式】 [成分（A)之環氧樹脂] -8- 200923007 本發明中之成分（A)之環氧樹脂並無特別限定，可 舉例爲例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚 S型環氧樹脂、苯酚酚醛清漆型環氧樹脂、第三丁基鄰苯 二酚型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、縮水 甘油胺型環氧樹脂、甲苯酚酚醛清漆型環氧樹脂、聯苯型 環氧樹脂、線狀脂肪族環氧樹脂、脂環式環氧樹脂、雜環 式環氧樹脂、含有螺環之環氧樹脂、鹵化環氧樹脂等。 環氧樹脂由耐熱性、絕緣信賴性、與金屬膜之密著性 之觀點觀之，該等中，較好爲雙酚A型環氧樹脂、萘酚型 環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂、具有丁二烯 構造之環氧樹脂。具體而言，舉例有液狀雙酚A型環氧樹 脂（日本環氧樹脂（股）製之「Epicote 828EL」（ jER828EL))、萘型2官能基環氧樹脂（大日本油墨化學 工業（股）製之「HP4032」、「HP4032D」）、萘型4官 能環氧樹脂（大曰本油墨化學工業（股）製之「HP4 700」 )、萘酚型環氧樹脂（東都化成（股）製「ESN-47SV」 )、含有丁二烯構造之環氧樹脂（Daicel化學工業（股） 製「PB_3 600」）、具有聯苯構造之環氧樹脂（日本化藥 (股）製「NC3000H」' 「NC3000L」，日本環氧樹脂（ 股）製「YX4000」）等。 環氧樹脂可單獨使用一種，亦可兩種以上倂用，但通 常含有一分子中具有2個以上環氧基之環氧樹脂。以環氧 樹脂組成物之不揮發成分做爲100質量％時’較好至少50 質量％以上爲一分子中具有2個以上環氧基之環氧樹脂。 200923007 再者，較佳樣態係含有一分子中具有2個以上環氧基且在 溫度20°C爲液狀之芳香族系環氧樹脂之環氧樹脂以及一分 子中具有3個以上環氧基且在溫度2 or爲固體狀之芳香族 系環氧樹脂。又，本發明中所謂之芳香族系環氧樹脂，意 指其分子內具有芳香環骨架之環氧樹脂。又環氧當量（ g/eq)意指每1環氧基之分子量。至於環氧樹脂，於使用 液狀環氧樹脂與固形環氧樹脂時，於環氧樹脂組成物以接 著薄膜形態使用時’於可形成顯示充分可撓性、操作性優 異之接著薄膜之同時，亦可提高環氧樹脂組成物之硬化物 的斷裂強度，且提高多層印刷電路板之耐久性。 又’作爲環氧樹脂，於倂用液狀環氧樹脂及固形環氧 樹脂時’其調配比例（液狀：固形）以質量比計，爲1 : 0 · 3〜1 : 2之範圍較佳。液狀環氧樹脂之比例若在該範圍內 ’則環氧樹脂組成物之黏度不會提高，以接著薄膜的形態 使用時’於真空層合時之脫氣性降低而不容易發生空隙。 又真空層合時保護薄膜或支持薄膜之剝離性不會降低，或 硬化後之耐熱性不會降低。又，於環氧樹脂組成物之硬化 物可獲得充分之斷裂強度。另一方面，若固形環氧樹脂之 比例在該範圍內’以接著薄膜形態使用時，可獲得充分的 可撓性’操作性良好’於層合之際可獲得充分的流動性。 本發明之環氧樹脂組成物中，以環氧樹脂組成物之不 揮發成分做爲100質量％時，環氧樹脂之含量較好爲 1 0〜50質量％ ’更好爲20〜40質量％，最好爲20〜35質量％ 。環氧樹脂（A )的含量若在此範圍內，則樹脂組成物之 -10- 200923007 硬化性良好。 [成分（B)之環氧硬化劑] 作爲於本發明中使用之環氧硬化劑 明效果而言，較好爲選自酚系硬化劑、 性酯系硬化劑之一種以上所構成之環氧 硬化劑、萘酚系硬化劑，就耐熱性、耐 最好爲具有酚醛清漆構造之酚系硬化劑 造之萘酚系硬化劑。此種具有酚醛清漆 或具有酚醛清漆構造之萘酚系硬化劑之 如 MEH-7700、MEH-7810、MEH- 7 8 5 1 製）、NHN、CBN、GPH(日本化藥（ 、SN180 、 SN190 、 SN475 、 SN485 、 SN3 95 (東都化成（股）製）、LA705 2 油墨化學工業（股）製）等。作爲活性 有 EXB-945 1、EXB-9460 (大日本油墨 )、DC808 (日本環氧樹脂（股）製） 化劑可使用1種或2種以上倂用，但尤 硬化劑之反應性較差故較好倂用酚系瑪 硬化劑。 於本發明，環氧樹脂組成物中之環 常環氧硬化劑之反應基合計數相對於環 在之環氧基之合計數之比例，於以環氧 ’較好成爲1: 〇·5~1: 1.1之量，更好 ，就充分發揮本發 萘酚系硬化劑及活 硬化劑。作爲酚系 水性之觀點而言， 或具有酚醛清漆構 構造之酚系硬化劑 市售品，舉例有例 (明和化成（股） 股）製）、SN170 SN495 、 SN375 、 、LA705 4 (大曰本 酯系硬化劑，舉例 化學工業（股）製 等。於本發明，硬 其是由於活性酯系 ί化劑及/或萘酚系 氧硬化劑之量，通 氧樹脂組成物中存 基合計數作爲1時 爲該比例成爲1 : -11 - 200923007 0.5~1 : 0.9之量。又所謂環氧樹脂組成物中存 之合計數’爲所有環氧樹脂中各環氧樹脂之固 以環氧當量之値之合計値，而所謂環氧硬化劑 活性羥基、活性酯基等）之合計數，爲所有硬 化劑之固形分質量除以反應基當量之値之合計 硬化劑之含量在此較佳範圍內，使環氧樹脂組 得之硬化物之耐熱性變得不足。 [成分（C)之苯氧基樹脂及/或聚乙烯縮醛 於本發明，苯氧基樹脂及/或聚乙烯縮醛 接著薄膜賦予充分可撓性及調整粗糙化性之目 作爲苯氧基樹脂之具體例舉例有東都化成 FX280、FX293 ;日本環氧樹脂（股）製之 YX6 95 4、YL6974等。聚乙烯縮醛樹脂並無特 較好爲聚乙烯縮丁醛樹脂。作爲聚乙烯縮醛樹 舉例有電氣化學工業（股）製之電化縮丁鹿 5000-A、6000-C、6000-EP;積水化學工業（月: REC BH系列、BX系歹U、KS系歹[J、BL系歹[J、 〇 該聚乙烯縮醛以玻璃轉移溫度爲80°C以上 此處所謂「玻璃轉移溫度」係依據JIS K 7197 法加以決定。又，玻璃轉移溫度高於分解溫度 無法觀察到玻璃轉移溫度時，可以分解溫度作 之玻璃轉移溫度。又，所謂分解溫度係定義爲 在之環氧基 形分質量除 之反應基（ 化劑中各硬 値。藉由使 成物硬化所 樹脂] 阓脂係爲對 的而使用。 (股）製之 YX8100 、 別限制，但 脂之具體例 ί 4000-2 ' € )製之S-ΒΜ系列等 者爲最佳。 所記載之方 而在實際上 爲本發明中 依據Π S Κ 200923007 7 1 2 0所記載之方法測定時質量減少率爲5 %時之溫度。 本發明之環氧樹脂組成物中，以環氧樹脂組成物之不 揮發成分作爲100質量％時，該苯氧基樹脂及/或聚乙烯縮 醛樹脂之含量較好在2〜20質量％之範圍。藉由此其在該範 圍內，可獲得充分的可撓性、操作性亦良好，由電鍍所形 成之導體層之剝離強度變充分。又若超過20質量％ ’層合 時無法獲得充分的流動性，有粗糙度變得過大的傾向。 [成分（D)之含磷苯并噁嗪化合物] 作爲於本發明中使用之含磷苯并噁嗪化合物，最好爲 以下式（1 )表示之含磷苯并噁嗪化合物（參考WO/2008/ 010429) ° [化1][3] The epoxy resin composition according to the above [1] or [2], wherein the epoxy curing agent is one or more selected from the group consisting of a phenolic curing agent, a naphthol curing agent, and an active ester curing agent. Epoxy hardener. [4] The epoxy resin composition according to any one of the above [1] to [3], wherein the non-volatile component of the epoxy resin composition is 1% by mass, the component (A) The content is 10 to 50% by mass, the content of the component (C) is 2 to 20% by mass, and the content of the component (D) is 2 to 20% by mass, and the reactive group of the epoxy hardener is composed with respect to the epoxy resin. The ratio of one epoxy group present in the material is 1: 0.5 to 1: 1.1. [5] The epoxy resin composition according to any one of the above [1] to [4] further comprising an inorganic chelating agent. [6] The epoxy resin composition according to the above [5], wherein the content of the inorganic cerium filler is from 10 to 60% by mass based on the nonvolatile component of the epoxy resin composition. [7] A film which is formed by laminating a layer of the epoxy resin composition according to any one of the above [1] to [6]. [8] A prepreg according to any one of the above [1] to [6], wherein the flaky fiber base material comprising the fibers is impregnated with the epoxy resin composition according to any one of the above [1] to [6]. [9] A multilayer printed wiring board comprising the insulating layer formed of the cured product of the epoxy resin composition according to any one of the above [1] to [6]. [10] A method of manufacturing a multilayer printed circuit board, comprising the steps of forming an insulating layer on an inner layer circuit substrate and forming a conductor layer on the insulating layer, wherein the insulating layer is such that [1] The epoxy resin composition according to any one of [6] is formed by thermosetting, and the conductor layer is formed by electroplating on the roughened surface of the surface of the insulating layer which has been roughened. -7- 200923007 [11] A method of manufacturing a multilayer printed circuit board having a step of forming an insulating layer on an inner layer circuit substrate and a step of forming a conductor layer on the insulating layer, characterized by having an insulating layer forming step a step of roughening the insulating layer and a step of plating the rough surface; the insulating layer forming step is a step of laminating a film forming a layer on the support film of the above [7] on the inner layer circuit substrate And a step of thermally hardening the epoxy resin composition. [1] A method of manufacturing a multilayer printed circuit board, comprising the steps of forming an insulating layer on an inner layer circuit substrate and forming a conductor layer on the insulating layer, wherein the insulating layer is in an inner layer The prepreg according to the above [8] is laminated on the circuit board, and the epoxy resin composition is thermally cured. The conductor layer is formed by plating on the roughened surface of the surface of the insulating layer which has been roughened. [13] The method for producing a multilayer printed wiring board according to any one of [10] to [12] wherein the roughening treatment is carried out using an alkaline permanganic acid solution. [Effect of the Invention] According to the present invention, it is possible to introduce into a multilayer printed circuit board that even if the roughness of the roughened surface after the roughening treatment is relatively small, the conductor layer formed by the plating has excellent adhesion strength and excellent flame retardancy. Insulation layer. [Embodiment] [Epoxy Resin of Component (A)] -8- 200923007 The epoxy resin of the component (A) in the present invention is not particularly limited, and examples thereof include, for example, bisphenol A type epoxy resin and bisphenol F. Epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, tert-butyl catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, glycidylamine Epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiral ring , halogenated epoxy resin, etc. The epoxy resin is preferably a bisphenol A type epoxy resin, a naphthol type epoxy resin, or a naphthalene type epoxy resin from the viewpoints of heat resistance, insulation reliability, and adhesion to a metal film. , biphenyl type epoxy resin, epoxy resin with butadiene structure. Specific examples include liquid bisphenol A type epoxy resin ("Epicote 828EL" (jER828EL) manufactured by Nippon Epoxy Co., Ltd.), and naphthalene type 2-functional epoxy resin (Daily Ink Chemical Industry Co., Ltd.) "HP4032" and "HP4032D"), naphthalene type 4-functional epoxy resin ("HP4 700" manufactured by Otsuka Ink Chemical Industry Co., Ltd.), and naphthol type epoxy resin (Dongdu Chemical Co., Ltd.) "ESN-47SV"), epoxy resin containing butadiene structure ("PB_3 600" manufactured by Daicel Chemical Industry Co., Ltd.), epoxy resin having biphenyl structure ("NC3000H" manufactured by Nippon Kayaku Co., Ltd." "NC3000L", "YX4000" made by Japan Epoxy Co., Ltd.). The epoxy resin may be used singly or in combination of two or more kinds, but usually contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin composition is 100% by mass, it is preferably at least 50% by mass or more of an epoxy resin having two or more epoxy groups in one molecule. 200923007 Further, a preferred embodiment is an epoxy resin having an aromatic epoxy resin having two or more epoxy groups in a liquid state at a temperature of 20 ° C and having three or more epoxy groups per molecule. Aromatic epoxy resin with a base at a temperature of 2 or a solid. Further, the term "aromatic epoxy resin" as used in the present invention means an epoxy resin having an aromatic ring skeleton in its molecule. Further, the epoxy equivalent (g/eq) means the molecular weight per 1 epoxy group. In the case of using an epoxy resin and a solid epoxy resin, when the epoxy resin composition is used in the form of a film, it can form a film which exhibits sufficient flexibility and excellent handleability. It is also possible to increase the breaking strength of the cured product of the epoxy resin composition and to improve the durability of the multilayer printed circuit board. Further, as the epoxy resin, when the liquid epoxy resin and the solid epoxy resin are used, the mixing ratio (liquid form: solid form) is preferably in the range of 1:0 · 3 to 1 : 2 by mass ratio. . When the ratio of the liquid epoxy resin is within this range, the viscosity of the epoxy resin composition is not increased, and when it is used in the form of a film, the degassing property at the time of vacuum lamination is lowered, and voids are less likely to occur. Further, the peeling property of the protective film or the supporting film at the time of vacuum lamination is not lowered, or the heat resistance after hardening is not lowered. Further, sufficient fracture strength can be obtained in the cured product of the epoxy resin composition. On the other hand, when the ratio of the solid epoxy resin is within this range', when it is used in the form of a film, sufficient flexibility can be obtained, and the workability is good. At the time of lamination, sufficient fluidity can be obtained. In the epoxy resin composition of the present invention, when the nonvolatile content of the epoxy resin composition is 100% by mass, the content of the epoxy resin is preferably from 10 to 50% by mass, more preferably from 20 to 40% by mass. , preferably 20 to 35 mass%. When the content of the epoxy resin (A) is within this range, the resin composition is excellent in the hardening property of -10-200923007. [Epoxy curing agent for component (B)] The epoxy curing agent used in the present invention is preferably an epoxy resin selected from one or more selected from the group consisting of a phenolic curing agent and a fatty ester curing agent. The hardener and the naphthol-based curing agent are heat-resistant and resistant to a naphthol-based curing agent which is preferably a phenol-based curing agent having a novolak structure. Such a naphthol-based hardener having a novolak or a novolac structure such as MEH-7700, MEH-7810, MEH-7815, NNH, CBN, GPH (Nippon Chemicals (, SN180, SN190, SN475, SN485, SN3 95 (manufactured by Tosho Kasei Co., Ltd.), LA705 2 Ink Chemical Industry Co., Ltd., etc. As active, there are EXB-945 1, EXB-9460 (Daily Ink), DC808 (Japanese epoxy resin). (Production) The chemical agent may be used singly or in combination of two or more kinds, but in particular, the reactivity of the curing agent is poor, so that a phenol-based curing agent is preferably used. In the present invention, the epoxy resin composition is often used. The ratio of the total number of the reactive groups of the epoxy curing agent to the total number of epoxy groups in the ring is preferably from the amount of the epoxy group of 1: 〇·5 to 1:1.1. A naphthol-based sclerosing agent and a sclerosing agent, and a phenolic-based sclerosing agent having a novolac structure, and a phenolic varnish-based sclerosing agent, exemplified by an example (Mingwa Kasei Co., Ltd.), SN170 SN495, SN375, and LA705 4 (large steroid ester hardeners, examples of chemical industry In the present invention, the amount of the active ester-based phthalic acid and/or the naphthol-based oxygen curing agent is hard. When the total number of bases in the oxygen-containing resin composition is 1, the ratio becomes 1: -11. - 200923007 0.5~1 : The amount of 0.9. The total count of the epoxy resin composition is the sum of the epoxy equivalents of the epoxy resins in all epoxy resins, and the so-called epoxy hardening. The total amount of the active hydroxyl group, the active ester group, etc., is the total amount of the solid content of all the hardeners divided by the equivalent of the reactive base, and the content of the hardener is within the preferred range, so that the cured epoxy resin is obtained. The heat resistance becomes insufficient. [Phenyloxy resin and/or polyvinyl acetal of component (C) In the present invention, the phenoxy resin and/or the polyvinyl acetal adhesive film imparts sufficient flexibility and adjusts roughening properties as a phenoxy group. Specific examples of the resin include Dongdu Chemical FX280 and FX293, and YX6 95 4 and YL6974 manufactured by Japan Epoxy Resin Co., Ltd. The polyvinyl acetal resin is not particularly preferably a polyvinyl butyral resin. As a polyvinyl acetal tree, there are electro-chemical industry (stock) electroformation Dinglu 5000-A, 6000-C, 6000-EP; Sekisui Chemical Industry (month: REC BH series, BX system 歹U, KS system 歹[J, BL system 歹 [J, 〇 The polyvinyl acetal has a glass transition temperature of 80 ° C or higher. The so-called "glass transition temperature" is determined according to JIS K 7197. Further, the glass transition temperature is higher than the decomposition temperature. When the glass transition temperature cannot be observed, the temperature at which the glass transition temperature can be decomposed can be decomposed. The so-called decomposition temperature is defined as the amount of the epoxy group divided by the reactive group (the hard acid in the chemical agent. Resin resin] The resin is used as a pair. The YX8100 made by (share) is not limited, but the specific example of the grease ί 4000-2 ' € ) is the best S-ΒΜ series. In the present invention, the temperature at which the mass reduction rate is 5% is determined according to the method described in Π S Κ 200923007 7 1 2 0. In the epoxy resin composition of the present invention, the epoxy resin composition is used. The phenoxy tree when the nonvolatile component is 100% by mass The content of the polyvinyl acetal resin is preferably in the range of 2 to 20% by mass, whereby within this range, sufficient flexibility and workability can be obtained, and the conductor layer formed by electroplating can be obtained. When the amount is more than 20% by mass, when sufficient liquidity is not obtained at the time of lamination, the roughness tends to be too large. [The phosphorus-containing benzoxazine compound of the component (D)] As the present invention The phosphorus-containing benzoxazine compound to be used is preferably a phosphorus-containing benzoxazine compound represented by the following formula (1) (refer to WO/2008/010429) ° [Chemical Formula 1]

此化合物含有磷，而可作爲不含鹵素之難燃劑之功能 。且與環氧樹脂具有反應性。作爲市售者，舉例有昭和高 分子（股）製之HF-B〇Z06(以式（1)表示之含磷苯并嚼 嗪化合物之二噁烷溶液）、HFB-2006M (以式（1 )表示 之含磷苯并噁嗪化合物之1-甲氧基-2 -丙醇溶液）等。本 發明之環氧樹脂組成物中，以環氧樹脂組成物之不揮發成 分作爲100質量％時，成分（D)之含量較好在2〜20質量 %之範圍，更好爲2〜10質量％，最好爲3〜6質量％。藉由 200923007 使成分（D)之含量於2〜20質量％，可提高硬化物之難燃 性及低吸濕性。 本發明之環氧樹脂組成物中，爲降低熱膨脹率等之目 的亦可進而含有無機塡充劑。作爲無機塡充劑，可舉例有 例如氧化矽、氧化鋁、硫酸鋇、滑石、黏土、雲母粉、氫 氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、 硼酸鋁、鈦酸鋇、鈦酸鋸、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧 化鈦、銷酸鋇、銷酸鈣等，該等中最好爲無定形氧化矽、 熔融氧化矽、結晶氧化矽、合成氧化矽等之氧化矽。作爲 氧化矽較好爲球狀者。無機塡充劑之平均粒徑較好爲1 μπι 以下，更好爲0 · 8 μιη以下，最好爲0.7 μιη以下。平均粒徑 超過1 μηι時’由電鍍所形成之導體層之剝離強度有降低之 傾向。又’無機塡充劑之平均粒徑若過小，則環氧樹脂組 成物作爲樹脂清漆時，由於清漆黏度上昇而有操作性降低 之傾向’故較好平均粒徑爲〇.〇 5 μιη以上。又，爲使無機 塡充劑提高耐濕性，較好爲以環氧矽烷偶合劑、胺基矽烷 ί禹合劑' Μ酸酯系偶合劑等表面處理劑進行表面處理者。 上述無機塡充劑之平均粒徑係依據Mie散射理論藉由 雷射繞射·散射法測定。具體的雷射繞射粒度分布裝置， 以體積爲基準作成無機塡充劑之粒度分布，可以其中値粒 徑作爲平均粒徑加以測定。測定樣品可較好使用藉由超音 波使無機塡充劑分散於水中者。至於雷射繞射粒度分布測 定裝置’可使用堀場製作所（股）製之LA- 500等。 於1周配該無機塡充劑時於環氧樹脂組成物（不揮發成 -14- 200923007 分1 00質量％ )中含量係依據樹脂組成物所要求之特定而 有不同，但較好爲10〜60質量％，更好爲15〜50質量％， 最好爲15~45質量％。 本發明之環氧樹脂組成物爲提高硬化物之機械強度’ 亦可以應力緩和效果等之目的而含有固體狀橡膠粒子。本 發明中之橡膠粒子爲不溶解於調製環氧樹脂組成物時之有 機溶劑，且與環氧樹脂等之樹脂組成物中之成分亦不相溶 者。因此，本發明中橡膠粒子於環氧樹脂組成物之清漆中 係以分散狀態存在。此等橡膠粒子，一般係大至橡膠成分 之分子量不溶解於有機溶劑或樹脂中之程度，而調製爲粒 子狀。作爲橡膠粒子，舉例有例如芯殼型橡膠粒子、交聯 丙烯腈丁二烯橡膠粒子、交聯苯乙烯丁二烯橡膠粒子、丙 烯酸橡膠粒子等。芯殼型橡膠粒子爲粒子具有芯層及殼層 之橡膠粒子，舉例有例如外層之殼層爲玻璃狀聚合物’內 層之芯層爲橡膠狀聚合物所構成之2層構造，或外層之殻 層爲玻璃狀聚合物、中間層爲橡膠狀聚合物、芯層爲玻璃 狀聚合物所構成之3層構造者。玻璃層係以甲基丙烯酸甲 酯之聚合物等所構成，橡膠狀聚合物層係例如以丙烯酸丁 酯聚合物（丁基橡膠）等構成。作爲芯殼型橡膠粒子之具 體例，舉例有 Staphyloid AC3832、AC3816N (GANZ 化成 (股）商品名）、Metablen KW-4426 (三菱 RAYON (股 )商品名）。丙烯腈丁二烯橡膠（NBR )粒子之具體例舉 例有XER-91 (平均粒徑〇_5μιη，JSR (股）製）等。苯乙 烯丁二烯橡膠（SBR)粒子之具體例舉例有XSK-500 (平 -15- 200923007 均粒徑0.5 μπι，JSR (股）製）等。丙烯酸橡膠粒子之具 體例可舉例有 Metablen W300A (平均粒徑 Ο.ΐμπι)、 W45 0A (平均粒徑0_5μιη )(三菱RAYON (股）商品名） 〇 所調配之橡膠粒子之平均粒徑較好在0.005〜Ιμιη之範 圍，更好爲0.2 ~ 0.6 μιη之範圍。本發明中橡膠粒子之平均 粒徑可使用動態光散射法加以測定。例如藉由超音波將橡 膠粒子均一分散於適當有機溶劑中，使用FPRA-1 000 (大 塚電子（股）製），以質量基準作成橡膠粒子之粒度分布 ，可測定其中値粒徑作爲平均粒徑。 調配該橡膠粒子時於於環氧樹脂組成物（不揮發成分 100質量％ )中含量較好爲1〜10質量％，更好爲2〜5質量 %。 本發明之環氧樹脂組成物亦可含有以調整硬化時間等 爲目的之硬化促進劑。作爲硬化促進劑，舉例有例如有機 V 膦化合物、咪唑化合物、胺基加成物化合物、3級胺化合 物等。作爲有機膦化合物之具體例，舉例有三苯膦（商品 名ΤΡΡ)、四苯基鐵四苯基硼酸鹽（商品名ΤΡΡ-Κ )、三 苯膦三苯基硼烷（商品名TPP-S)、三-對-甲苯基膦（ TPTP-S) ’以上爲北興化學工業（股）製等。作爲咪唑化 合物之具體例，舉例有2-甲基咪唑（商品名Curezol 2ΜΖ )、2-乙基-4-甲基咪唑（商品名2E4MZ) 、2-脲基咪唑（ 商品名C11Z) 、1-氰基乙基-2-脲基咪哩（商品名C11Z- CN ) 、1-氰基乙基-2-脲基咪唑鑰偏苯三酸鹽（商品名 -16- 200923007This compound contains phosphorus and functions as a halogen-free flame retardant. And reactive with epoxy resin. As a commercial product, HF-B〇Z06 (a dioxane solution of a phosphorus-containing benzoxazine compound represented by the formula (1)) of the Showa Polymer Co., Ltd., HFB-2006M (for the formula (1) ) a solution of a phosphorus-containing benzoxazine compound in 1-methoxy-2-propanol). In the epoxy resin composition of the present invention, when the nonvolatile content of the epoxy resin composition is 100% by mass, the content of the component (D) is preferably in the range of 2 to 20% by mass, more preferably 2 to 10% by mass. %, preferably 3 to 6 mass%. By the content of the component (D) in the range of 2 to 20% by mass in 200923007, the flame retardancy and low hygroscopicity of the cured product can be improved. The epoxy resin composition of the present invention may further contain an inorganic chelating agent for the purpose of lowering the coefficient of thermal expansion and the like. As the inorganic chelating agent, for example, cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Barium titanate, titanate saw, calcium titanate, magnesium titanate, barium titanate, titanium oxide, strontium strontium sulphate, calcium sulphate, etc., among which amorphous yttrium oxide, yttrium oxide yttrium, crystalline yttrium oxide And synthesizing cerium oxide such as cerium oxide. As the cerium oxide, it is preferably spherical. The average particle diameter of the inorganic chelating agent is preferably 1 μπ or less, more preferably 0·8 μηη or less, and most preferably 0.7 μηη or less. When the average particle diameter exceeds 1 μm, the peeling strength of the conductor layer formed by electroplating tends to decrease. Further, when the average particle diameter of the inorganic chelating agent is too small, the epoxy resin composition is used as a resin varnish, and the varnish viscosity tends to decrease, and the operability is lowered. Therefore, the average particle diameter is preferably 〇.〇 5 μmη or more. Further, in order to improve the moisture resistance of the inorganic chelating agent, it is preferred to carry out surface treatment with a surface treating agent such as an epoxy decane coupling agent or an amino decane chelating agent phthalate coupling agent. The average particle diameter of the above inorganic chelating agent is measured by a laser diffraction/scattering method in accordance with the Mie scattering theory. A specific laser diffraction particle size distribution device is used to prepare a particle size distribution of an inorganic chelating agent based on a volume, wherein the ruthenium particle diameter can be measured as an average particle diameter. The sample can be preferably used by dispersing an inorganic chelating agent in water by ultrasonic waves. As for the laser diffraction particle size distribution measuring device, the LA-500 manufactured by Horiba, Ltd. can be used. The content of the epoxy resin composition (non-volatile to -14, 200923007, 100% by mass) in the case of the inorganic chelating agent at one week varies depending on the specificity of the resin composition, but is preferably 10 ～60% by mass, more preferably 15 to 50% by mass, most preferably 15 to 45% by mass. The epoxy resin composition of the present invention contains solid rubber particles for the purpose of improving the mechanical strength of the cured product. The rubber particles in the present invention are organic solvents which are insoluble in the preparation of the epoxy resin composition, and are incompatible with components in the resin composition such as epoxy resin. Therefore, in the present invention, the rubber particles are present in a dispersed state in the varnish of the epoxy resin composition. These rubber particles are generally prepared in a granular form to such an extent that the molecular weight of the rubber component is not dissolved in the organic solvent or the resin. Examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles in which the particles have a core layer and a shell layer, and for example, a shell layer of an outer layer is a two-layer structure in which a core layer of a glassy polymer 'inner layer is a rubbery polymer, or an outer layer The shell layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a three-layer structure composed of a glassy polymer. The glass layer is composed of a polymer of methyl methacrylate or the like, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). As a specific example of the core-shell type rubber particles, Staphyloid AC3832, AC3816N (GANZ Chemical Co., Ltd.), Metablen KW-4426 (Mitsubishi RAYON (trade name) trade name) are exemplified. Specific examples of the acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle diameter 〇 5 μmη, manufactured by JSR Co., Ltd.). Specific examples of the styrene-butadiene rubber (SBR) particles include XSK-500 (flat -15-200923007 average particle diameter 0.5 μπι, manufactured by JSR Co., Ltd.). Specific examples of the acrylic rubber particles include Metablen W300A (average particle diameter Ο.ΐμπι), W45 0A (average particle diameter 0_5μιη) (Mitsubishi RAYON (trade name) trade name), and the average particle diameter of the rubber particles is preferably The range of 0.005 to Ιμιη is more preferably in the range of 0.2 to 0.6 μηη. The average particle diameter of the rubber particles in the present invention can be measured by dynamic light scattering. For example, by uniformly dispersing rubber particles in an appropriate organic solvent by ultrasonic waves, using FPRA-1 000 (manufactured by Otsuka Electronics Co., Ltd.), the particle size distribution of the rubber particles is determined on a mass basis, and the niobium particle diameter can be measured as an average particle diameter. . When the rubber particles are blended, the content of the epoxy resin composition (nonvolatile content: 100% by mass) is preferably from 1 to 10% by mass, more preferably from 2 to 5% by mass. The epoxy resin composition of the present invention may contain a curing accelerator for the purpose of adjusting the curing time and the like. The hardening accelerator may, for example, be an organic V phosphine compound, an imidazole compound, an amine-based adduct compound, a tertiary amine compound or the like. Specific examples of the organic phosphine compound include triphenylphosphine (trade name ΤΡΡ), tetraphenyl iron tetraphenyl borate (trade name: ΤΡΡ-Κ), and triphenylphosphine triphenyl borane (trade name TPP-S). , Tri-p-tolylphosphine (TPTP-S) 'The above is the Beixing Chemical Industry Co., Ltd. system. Specific examples of the imidazole compound include 2-methylimidazole (trade name: Curezol 2®), 2-ethyl-4-methylimidazole (trade name: 2E4MZ), 2-ureidoimidazole (trade name: C11Z), and 1- Cyanoethyl-2-ureidopyridinium (trade name C11Z-CN), 1-cyanoethyl-2-ureidoimidazole key trimellitate (trade name-16-200923007

Cl 1Z-CNS ) 、2,4-二胺基-6-[2’-脲基咪唑基-(丨’）]-乙 基-s-三嗪（商品名 C11Z-A) 、2MZ-OK、2,4-二胺基-6- [2’甲基咪唑基-(1，）]-乙基-s -三嗪異氰尿酸加成物（商 品名 2MA-OK) 、2 -苯基-4,5 -二羥基甲基咪唑（商品名 2PHZ )，以上爲四國化成工業（股）製等。胺基加成物化 合物之具體例舉例爲NOVACURE (旭化成工業（股）商 品名）、FUZICURE (富士化成工業（股）商品名）等。3 級胺化合物之具體例舉例有DBU ( 1,8-二氮雜雙環[5,4,0] 十一碳-7-烯）等。本發明之環氧樹脂組成物中，硬化促進 劑之含量，於環氧樹脂組成物中所含之環氧樹脂與酚性硬 化劑總量作爲1 〇〇質量％ (不揮發成分）時，通常以 0.1〜5質量％之範圍使用。 本發明之環氧樹脂組成物，在不損及本發明硬化之範 圍內亦可含有（D )成分以外之難燃劑。作爲難燃劑，舉 例有例如有機磷系難燃劑、有機含氮磷化合物、氮化合物 、矽氧系難燃劑、金屬氫氧化物等。 本發明之環氧樹脂組成物，在發揮本發明效果之範圍 內，亦可含有上述以外之其他樹脂。作爲其他樹脂，舉例 有氰酸酯樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺、聚醚颯樹 脂、聚颯樹脂等。 本發明之環氧樹脂組成物，在發揮本發明效果之範圍 內，亦可含有上述以外之其他樹脂添加劑。作爲樹脂添加 劑，舉例有例如矽粉、耐綸粉、氟系粉等之有機塡充劑， Orben、Benton等之增黏劑’矽系、氟系、高分子系之消 -17- 200923007 泡劑或平流劑，咪唑系、噻唑系、三唑系、矽烷偶合劑等 之密著性賦予劑、酞青藍、酞青綠、碘綠、顏料黃、碳黑 等著色劑等。 本發明之環氧樹脂組成物’可塗佈在支持薄膜上形成 樹脂組成物層而成爲多層印刷電路板用之接著薄膜，或亦 可於由纖維所構成之薄片狀纖維基材中含浸該樹脂組成物 ，成爲多層印刷電路板之層間絕緣層用之預浸片。本發明 之樹脂組成物可塗佈在電路基板上形成絕緣層，但在工業 上，一般係作爲接著薄膜或預浸片形態使用於形成絕緣層 〇 本發明之接著薄膜可藉由本技藝者已知方法，例如將 樹脂組成物溶解於有機溶劑中調製樹脂清漆，以支持薄膜 作爲支持體，塗佈該樹脂清漆，進而加熱或吹熱風而使有 機溶劑乾燥，形成樹脂組成物層而製造。 作爲有機溶劑，可舉例爲例如丙酮、甲基乙基酮、環 己酮等酮類；乙酸乙酯、乙酸丁酯、溶纖素乙酸酯、丙二 醇單甲基醚乙酸酯、卡必醇乙酸酯等之乙酸醋類；溶纖素 、丁基卡必醇等之卡必醇類；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。可使用1種有機溶劑亦可組合2種以上使 用。 乾燥條件並無特別限制’可乾燥成有機溶劑對樹脂組 成物層之含有比例通常在1 0質量％以下’更好爲5質量％ 以下。乾燥條件可藉由簡單實驗而設定適宜、適當之乾燥 -18- 200923007 條件。雖隨著清漆中有機溶劑量而異，但例如含有30〜60 質量％之有機溶劑之清漆係在50〜150°C乾燥3~10分鐘左 右。 於接著薄膜上形成之樹脂組成物層之厚度通常爲導體 層厚度以上。由於形成有電路基板之導體層之厚度通常爲 5〜70 μηι之範圍，故樹脂組成物層之厚度較好具有 10〜ΙΟΟμηι之厚度。樹脂組成物層亦可用後述之保護薄膜 進行保護。藉由以保護薄膜保護，可防止污物等附著於樹 脂組成物層表面或損傷。 本發明中作爲支持薄膜以及保護薄膜可舉例爲聚乙烯 、聚丙烯、聚氯乙烯等之聚烯烴之薄膜，聚對苯二甲酸乙 二酯（以下有時簡稱「PET」）、聚萘二甲酸乙二酯等之 聚酯之薄膜，聚碳酸酯薄膜、聚醯亞胺薄膜，可進而舉例 有離型紙或銅箔、鋁箔等之金屬箔等。又，支持薄膜及保 護薄膜經霧化處理、電暈處理以外，亦可施加離型處理。 支持薄膜厚度並無特別限制，通常爲10〜15 Ομιη，較 好爲25〜5 Ομιη之範圍。又保護薄膜厚度並無特別限制，通 常以1〜4 0μιη，更好以1 0〜30μιη之範圍使用。又，如後述 ，於接著薄膜之製造步驟中作爲支持體使用之支持薄膜， 亦可使用作爲保護樹脂組成物層表面之保護薄膜。 本發明中之支持薄膜，層合於電路基板上之後，或藉 由加熱硬化而形成絕緣層之後，予以剝離。接著薄膜加熱 硬化後若剝離支持薄膜，則可防止在硬化步驟中污物之附 著，又可提高硬化後絕緣層之表面平滑性。硬化後剝離時 -19- 200923007 ，通常對支持薄膜預先施以離型處理。又，於支持薄膜上 形成之樹脂組成物層，較好形成爲層的面積比支持薄膜之 面積小。又接著薄膜可捲取爲輥筒狀後，予以保存、儲藏 〇 接著，對本發明之使用接著薄膜之本發明多層印刷電 路板之製造方法加以說明。樹脂組成物層以保護薄膜加以 保護之情況下將其剝離後，以使樹脂組成物層直接接觸於 電路基板之方式，層合於電路基板之單面或雙面。本發明 之接著薄膜較好使用於藉由真空層合法以減壓下層合於電 路基板之方法。層合方法可爲批式亦可爲以輥之連續式。 又進行層合之前亦可視需要對接著薄膜及電路基板予以加 熱（預加熱）。 層合條件，壓著溫度（層合溫度）較好爲70~140°c， 壓著壓力較好爲 1 〜llkgf/cm2 ( 9.8xl04~107.9xl04N/m2) ，較好以空氣壓爲20mmHg ( 26.7hPa )以下之減壓下進行 層合。 真空層合可使用市售真空層合機進行。至於市售真空 層合機可舉例爲例如NICHIGO MORTON (股）製之真空 塗佈機、名機製作所（股）製之真空加壓式層合機、曰立 工業（股）製之輥式乾式塗佈機、日立AIC (股）製之真 空層合機等。 本發明中所謂之內層電路基板，主要是意指於玻璃環 氧、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之基板之單面或兩面上形成有經 -20- 200923007 圖型加工之導體層（電路）者。又導體層與絕緣層形成交 互層，成爲於單面或兩面上之經圖型加工之導體層（電路 )，於製造多層印刷電路板時，適合進而形成有絕緣層及 導體層之中間製造物亦包含於本發明之內層電路基板內。 關於內層電路基板，由絕緣層對內層電路基板之密著性之 觀點觀之，較好藉由黑化處理等對導體電路層表面預先施 加粗糙化處理。 如此將接著薄膜層合於電路基板上之後，剝離支持薄 膜之情況，可藉由剝離、熱硬化而在電路基板上形成絕緣 層。加熱硬化條件係在150 °C〜220 °C歷時20分鐘〜180分 鐘之範圍內選擇，更好在160°C〜200°C歷時30分鐘〜120 分鐘。 形成絕緣層後，於硬化前未剝離支持薄膜之情況，於 此進行剝離。接著於電路基板上形成之絕緣層上進行開孔 而形成埋孔、通孔。開孔係藉由例如鑽孔、雷射、電漿等 之已知方法，又依據必要可組合該等方法進行，但藉由碳 酸氣體雷射、YAG雷射等之雷射進行開孔較爲一般之方法 〇 接著，進行絕緣層表面之粗糙化處理。本發明中之粗 糙化處理通常較好以使用氧化劑之濕式粗糙化方法進行。 作爲氧化劑，舉例有過錳酸鹽（過錳酸鉀、過錳酸鈉等） 、重鉻酸鹽、臭氧、過氧化氫/硫酸、硝酸等。較好爲藉 由堆焊（built-up) method製造多層印刷電路板中絕緣層 粗糙化所廣泛使用之氧化劑，較好使用鹼性過錳酸溶液（ -21 - 200923007 例如過錳酸鉀、過錳酸鈉水溶液）進行粗糙化。 絕緣層表面經粗糙化處理之粗糙化面之粗糙度，於形 成微細配線方面，較好Ra値爲0 · 5 μιη以下。所謂Ra値爲 表示表面粗糙度之數値之一種，係稱爲算數平均粗糙度者 ，具體而言，係自測定區域內變化高度之絕對値之平均線 的表面測定之算數平均者。例如，可使用Veeco儀器公司 製WYKO NT3 3 00，以VSI接觸模式，自藉由50倍透鏡以 121μηι><92μπι爲測定範圍所得之數値而求得。 接著，於藉由粗糙化處理形成有凹凸錨定之樹脂組成 物層表面上，以組合無電解電鍍及電解電鍍之方法形成導 體層。又所謂導體層可爲形成逆圖型之電鍍光阻，僅以無 電解電鍍形成導體層者。又導體層形成後，藉由在 150〜200 °C退火（anneal) 20〜90分鐘，可使導體層之剝離 強度進一步提高並安定化。導體層之剝離強度較好爲 0.6kgf/cm 以上。 又，作爲對導體層圖型加工形成電路之方法，可使用 例如本技藝者已知之削減法（自全面貼銅之基板除去不要 部分而形成電路之方法）或半加成法（於絕緣體基板上自 後附加電路圖型之方法）等。 本發明之預浸片可將本發明之樹脂組成物藉由熱溶融 法或熔劑法含浸於由纖維等所構成之薄片狀纖維基材中， 藉由加熱使其半硬化而製造。亦即，本發明之樹脂組成物 可成爲含浸於由纖維所構成之薄片狀纖維基材中之狀態之 預浸片。 -22-Cl 1Z-CNS ), 2,4-diamino-6-[2'-ureidoimidazolyl-(丨')]-ethyl-s-triazine (trade name C11Z-A), 2MZ-OK, 2,4-Diamino-6-[2'methylimidazolyl-(1,)]-ethyl-s-triazine isocyanuric acid adduct (trade name 2MA-OK), 2-phenyl- 4,5-dihydroxymethylimidazole (trade name 2PHZ), the above is the Shikoku Chemical Industry Co., Ltd. system. Specific examples of the amine-based adduct compound are NOVACURE (Asahi Kasei Industrial Co., Ltd. product name), FUZICURE (Fuji Chemical Industry Co., Ltd. trade name), and the like. Specific examples of the tertiary amine compound are exemplified by DBU (1,8-diazabicyclo[5,4,0]undec-7-ene). In the epoxy resin composition of the present invention, the content of the hardening accelerator is usually 1% by mass (nonvolatile matter) of the total amount of the epoxy resin and the phenolic hardener contained in the epoxy resin composition. It is used in the range of 0.1 to 5 mass%. The epoxy resin composition of the present invention may contain a flame retardant other than the component (D) without damaging the hardening of the present invention. Examples of the flame retardant include, for example, an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a xenon-based flame retardant, and a metal hydroxide. The epoxy resin composition of the present invention may contain other resins than those described above within the range in which the effects of the present invention are exerted. Examples of the other resin include a cyanate resin, a polyimide resin, a polyamidoxime, a polyether eucalyptus, and a polyfluorene resin. The epoxy resin composition of the present invention may contain other resin additives than the above insofar as the effects of the present invention are exerted. Examples of the resin additive include organic chelating agents such as strontium powder, nylon powder, and fluorine-based powder, and tackifiers such as Orben and Benton, which are fluorene-based, fluorine-based, and polymeric-based -17-200923007 foaming agents. Or a leveling agent, a coloring agent such as an imidazole-based, a thiazole-based, a triazole-based or a decane coupling agent; a coloring agent such as indigo blue, indocyanine green, iodine green, pigment yellow or carbon black. The epoxy resin composition of the present invention can be applied to a support film to form a resin composition layer to form a film for a multilayer printed circuit board, or can be impregnated into a sheet-like fiber substrate composed of fibers. The composition is a prepreg for an interlayer insulating layer of a multilayer printed circuit board. The resin composition of the present invention can be applied to a circuit board to form an insulating layer, but industrially, it is generally used as an adhesive film or a prepreg sheet to form an insulating layer. The film of the present invention can be known by those skilled in the art. In the method, for example, the resin composition is dissolved in an organic solvent to prepare a resin varnish, and the film is supported as a support, and the resin varnish is applied, and the organic solvent is dried by heating or blowing hot air to form a resin composition layer. The organic solvent may, for example, be a ketone such as acetone, methyl ethyl ketone or cyclohexanone; ethyl acetate, butyl acetate, fibrin acetate, propylene glycol monomethyl ether acetate, carbitol. Acetic acid vinegar such as acetate; carbitol such as cellulase or butyl carbitol; aromatic hydrocarbon such as toluene or xylene; dimethylformamide, dimethylacetamide, A guanamine-based solvent such as N-methylpyrrolidone. One type of organic solvent may be used, or two or more types may be used in combination. The drying conditions are not particularly limited, and the content ratio of the organic solvent to the resin composition layer is usually 10% by mass or less, more preferably 5% by mass or less. Dry conditions can be set by appropriate experiment and appropriate drying -18-200923007 conditions. Although the amount of the organic solvent in the varnish varies, for example, the varnish containing 30 to 60% by mass of the organic solvent is dried at 50 to 150 ° C for about 3 to 10 minutes. The thickness of the resin composition layer formed on the subsequent film is usually equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer on which the circuit substrate is formed is usually in the range of 5 to 70 μm, the thickness of the resin composition layer preferably has a thickness of 10 to ΙΟΟμη. The resin composition layer can also be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dirt or the like from adhering to the surface or damage of the resin composition layer. In the present invention, as the support film and the protective film, a film of a polyolefin such as polyethylene, polypropylene or polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes referred to as "PET") or polynaphthalene dicarboxylic acid can be exemplified. A film of a polyester such as ethylene glycol ester, a polycarbonate film or a polyimide film may, for example, be a metal foil such as a release paper, a copper foil or an aluminum foil. Further, the support film and the protective film may be subjected to a release treatment in addition to atomization treatment or corona treatment. The thickness of the supporting film is not particularly limited and is usually 10 to 15 Å μm, preferably 25 to 5 Ο μηη. Further, the thickness of the protective film is not particularly limited, and it is usually used in the range of 1 to 40 μm, more preferably 10 to 30 μm. Further, as will be described later, a protective film used as a support for the support film may be used as a protective film for protecting the surface of the resin composition layer. The support film of the present invention is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. Then, if the support film is peeled off after the film is heated and hardened, the adhesion of the dirt in the hardening step can be prevented, and the surface smoothness of the insulating layer after hardening can be improved. When peeling after hardening -19- 200923007, the support film is usually preliminarily subjected to release treatment. Further, the resin composition layer formed on the support film is preferably formed such that the area of the layer is smaller than the area of the support film. Further, the film can be wound up in a roll shape, and then stored and stored. Next, a method of manufacturing the multilayer printed circuit board of the present invention using the film of the present invention will be described. When the resin composition layer is protected by a protective film, the resin composition layer is peeled off, and the resin composition layer is laminated on one side or both sides of the circuit board so as to directly contact the circuit board. The adhesive film of the present invention is preferably used in a method of laminating to a circuit substrate under reduced pressure by vacuum lamination. The lamination method may be batch or continuous in rolls. The subsequent film and circuit substrate may be heated (preheated) as needed before lamination. The lamination condition, the pressing temperature (laminating temperature) is preferably 70 to 140 ° C, and the pressing pressure is preferably 1 to llkgf/cm 2 ( 9.8 x 10 4 to 107.9 x 10 4 N/m 2 ), preferably 20 mmHg (for air pressure) ( Lamination was carried out under reduced pressure of 26.7 hPa. Vacuum lamination can be carried out using a commercially available vacuum laminator. As for the commercially available vacuum laminating machine, for example, a vacuum coating machine manufactured by NICHIGO MORTON Co., Ltd., a vacuum pressure laminator manufactured by a famous machine manufacturer, and a roll type dry type manufactured by Kyoritsu Kogyo Co., Ltd. A vacuum laminator made of a coater or a Hitachi AIC (share). The inner layer circuit substrate in the present invention mainly means a single side of a substrate such as a glass epoxy, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate. A conductor layer (circuit) processed by the pattern of -20-200923007 is formed on both sides. Further, the conductor layer and the insulating layer form an alternating layer, and the conductor layer (circuit) is patterned on one or both sides. When manufacturing the multilayer printed circuit board, it is suitable to form an intermediate layer of the insulating layer and the conductor layer. Also included in the inner layer circuit substrate of the present invention. Regarding the inner layer circuit board, from the viewpoint of the adhesion of the insulating layer to the inner layer circuit board, it is preferable to apply a roughening treatment to the surface of the conductor circuit layer by blackening treatment or the like. After the film is laminated on the circuit board in this manner, the supporting film is peeled off, and the insulating layer can be formed on the circuit board by peeling and heat curing. The heat hardening conditions are selected from 150 ° C to 220 ° C for a period of from 20 minutes to 180 minutes, more preferably from 160 ° C to 200 ° C for 30 minutes to 120 minutes. After the insulating layer was formed, the support film was not peeled off before the hardening, and peeling was performed there. Then, openings are formed in the insulating layer formed on the circuit substrate to form buried vias and via holes. The opening is performed by a known method such as drilling, laser, plasma, etc., and may be combined according to necessity, but the opening is performed by a laser such as a carbon dioxide gas laser or a YAG laser. General Method Next, the roughening treatment of the surface of the insulating layer is performed. The roughening treatment in the present invention is usually preferably carried out by a wet roughening method using an oxidizing agent. Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, and the like. Preferably, an oxidizing agent widely used for roughening an insulating layer in a multilayer printed circuit board by a built-up method is preferably used, and an alkaline permanganic acid solution is preferably used (-21 - 200923007, for example, potassium permanganate, The sodium manganate solution was roughened. The roughness of the roughened surface on which the surface of the insulating layer is roughened is preferably 0 to 5 μmη or less in terms of forming fine wiring. The Ra 値 is a type indicating the number of surface roughnesses, and is called the arithmetic mean roughness. Specifically, it is the arithmetic average of the surface measurement of the average line of the absolute height of the change height in the measurement region. For example, it can be obtained by using VYKO NT3 3 00 manufactured by Veeco Instruments Co., Ltd. in a VSI contact mode from a number obtained by a 50-fold lens at 121 μm><92 μm. Next, on the surface of the resin composition layer on which the unevenness is anchored by roughening treatment, a conductor layer is formed by a combination of electroless plating and electrolytic plating. Further, the conductor layer may be a plating resist which forms an inverse pattern, and only a conductor layer is formed by electroless plating. Further, after the conductor layer is formed, the peeling strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 °C for 20 to 90 minutes. The peeling strength of the conductor layer is preferably 0.6 kgf/cm or more. Further, as a method of forming a circuit for patterning a conductor layer, for example, a reduction method known in the art (a method of forming a circuit by removing a unnecessary portion from a copper-plated substrate) or a semi-additive method (on an insulator substrate) can be used. Since the method of attaching a circuit pattern, etc.). The prepreg of the present invention can be produced by impregnating the resin composition of the present invention with a sheet-like fibrous base material composed of fibers or the like by a hot melt method or a flux method, and semi-curing it by heating. That is, the resin composition of the present invention can be a prepreg impregnated in a state of a sheet-like fibrous base material composed of fibers. -twenty two-

200923007 至於由纖維構成之薄片狀纖維基材，可使用例 布或芳醯胺纖維等常作爲預浸片用纖維使用者。 熱熔融法有未將樹脂溶解於有機溶劑中，而將 時塗佈在與樹脂之剝離性良好之塗佈紙上，將其層 片狀纖維基材上，或藉由染料旋塗機直接塗佈等， 預浸片之方法。又溶劑法，可爲與接著薄膜同樣， 狀纖維基材浸漬於使樹脂溶解於有機溶劑所得之樹 中，使樹脂清漆含浸於薄片狀纖維基材中，隨後乾 法。 接著對使用本發明之預浸片製造本發明之多層 路板之方法加以說明。於電路基板上，將本發明之B 一片或視需要數片重疊，介以離型薄膜夾住金屬板右 加熱條件下加壓層合。壓力較好爲5〜40kgf/cm2 104 〜3 92 xl04N/m2)，較好溫度爲 120 〜200 °C ,時 2 0~ 100分鐘之範圍成型。又與接著薄膜同樣地藉由真 合法層合於電路基板上之後，藉由加熱硬化亦可製逶 。隨後，與上述同樣地，藉由氧化劑使硬化後之預浸 面粗糙化後，藉由電鍍形成導體層，而製造多層印刷 板。 以下’使用實施例及比較例更詳細說明本發明， 等不應以任何方式限制本發明。又，以下記載中，「 意指「質量份」。 〈實施例1&gt; ]玻璃 ί脂暫 Γ於薄 ί製造 F薄片 ί清漆 i之方 1刷電 ί浸片 i加壓 (49χ 間爲 ;空層 i而得 ί片表 丨電路 惟該 份」 -23- 200923007 30份液狀雙酹A型環氧樹脂（環氧當量丨80，日本環 氧樹脂（股）製「EPicote 828EL」）與30份聯苯型環氧 樹脂（環氧當量291’日本化藥（股）製「NC3000H」） 於15份甲基乙基酮（以下簡稱爲「MEK」）及15份環己 酮中邊攪拌邊加熱溶解。於其中’混合1 〇 〇份之萘酚系硬 化劑（東都化成（股）製之「SN48 5」’酚性羥基當量 215 )之固形分50%之MEK溶液、0.1份硬化觸媒（四國 化成工業（股）製’ 「2E4MZ」）、70份球形氧化矽（平 均粒徑0.5μπι，經胺基砂院處理之「SO-C2」，Admatechs (股）製）、20份聚乙烯縮丁醛樹脂溶液（玻璃轉移溫度 105°C，積水化學工業（股）製「KS-1」之固形分15%之 乙醇與甲苯之1: 1溶液）、20份苯氧基樹脂（分子量 3 8,000，日本環氧樹脂（股）製「YX6954」，不揮發分 30質量％之MEK與環己酮之1 : 1溶液）、8份之以式（1 )表示之含磷苯并噁嗪（昭和高分子（股）製之：^?-Β Ο Z 0 6，固形分6 5 %之二噁烷溶液），以高速旋轉混合機 均一分散，製作樹脂清漆。接著將此樹脂清漆以染料旋塗 機塗佈在聚對苯二甲酸乙二酯（厚38μιη)上，使乾燥後 之樹脂厚度成爲40 μηι，在80〜120 °C (平均1〇〇 °C )乾燥6 分鐘（殘留溶劑量約2質量％ )。接著於樹脂組成物表面 貼合厚度15μιη之聚丙烯薄膜同時捲取成輥筒狀。將輥筒 狀接著薄膜切成寬507mm，藉此獲得5 07mmx3 3 6mm大小 之薄片狀接著薄膜。 -24- 200923007 &lt;實施例2 &gt; 3〇份液狀雙酚A型環氧樹脂（環氧當量18〇，日本環 氧樹脂（股）製「Epicote 828EL」）與30份聯苯型環氧 樹脂（環氧當量291，日本化藥（股）製「NC3000H」） 於1 5份MEK及15份環己酮中邊攪拌邊加熱溶解。於其 中，混合8 0份之萘酚系硬化劑（東都化成（股）製之「 SN4 85」，酚性羥基當量2 1 5 )之固形分50%之MEK溶液 、1 5份活性酯系硬化劑（大日本油墨化學工業（股）製之 「EXB945 1」，活性基當量223，固形分爲65質量％之甲 苯溶液）、0.1份硬化觸媒（四國化成工業（股）製’ 「 2 E 4Μ Z」）、7 0份球形氧化矽（平均粒徑0 · 5 μιη，經胺基 矽院處理之「SO-C2」’ Admatechs (股）製）、20份聚 乙烯縮丁醛樹脂溶液（玻璃轉移溫度1 〇 5 °C ’積水化學工 業（股）製「KS-1」之固形分15 %之乙醇與甲苯之1:1 溶液）、20份苯氧基樹脂（分子量3 8,000，日本環氧樹 脂（股）製「YX6954」’不揮發分30質量％之MEK與環 己酮之1: 1溶液）、15份之以式（1)表示之含憐本并螺 嗪（昭和高分子（股）製之HF_B〇Z06，固形分65%之二 噁烷溶液），以高速旋轉混合機均一分散，製作樹目曰清漆 。接著使用此樹脂清漆與實施例1完全一樣地獲得接著薄 膜。 &lt;比較例1 &gt; 於實施例ί記載之樹脂清漆中，除不添加8份含磷苯 -25- 200923007 并噁嗪（昭和高分子（股）製之HF-BOZ06，固形分65% 之二噁烷溶液）以外，其餘完全相同，獲得接著薄膜。 &lt;比較例2 &gt; 30份液狀雙酚A型環氧樹脂（環氧當量180 ’日本環 氧樹脂（股）製「Epicote 82 8EL」）與30份含磷環氧樹 脂（環氧當量3 06，東都化成（股）製「FX289」）於15 份MEK及15份環己酮中邊攪拌邊加熱溶解。於其中’混 合1〇〇份之萘酚系硬化劑（東都化成（股）製之「SN485 」，酚性羥基當量215 )之固形分50%之MEK溶液、Ο」 份硬化觸媒（四國化成工業（股）製’ 「2E4MZ」）、70 份球形氧化砂（平均粒徑〇 . 5 μ m ’經胺基砂院處理之「 SO-C2」，Admatechs (股）製）、20份聚乙烯縮丁醛樹 脂溶液（玻璃轉移溫度105。(：，積水化學工業（股）製「 KS-1」之固形分15 %之乙醇與甲苯之1: 1溶液）、20份 苯氧基樹脂（分子量38,000，日本環氧樹脂（股）製「 YX6954」，不揮發分3 0質量％之MEK與環己酮之1 . 1 溶液），以高速旋轉混合機均一分散’製作樹脂清漆。接 著使用此樹脂清漆與實施例1完全一樣地獲得接著薄膜。 &lt;比較例3 &gt; 於實施例1記載之樹脂清漆中，除8份含磷苯并噁嗪 (昭和高分子（股）製之HF-BOZ06，固形分65%之一噁 烷溶液）變更爲8份磷系難燃劑（三光（股）製2HCA_ -26- 200923007 HQ-HS)以外’其餘完全相同’獲得接著薄膜。 &lt;剝離強度及Ra値測定用樣品之調製&gt; (1)層合板之底層處理 將形成內層電路之玻璃布基材環氧樹脂兩面貼銅層合 板[銅箔厚度18μιη，基板厚度0.3mm，松下電工（股）製 R5 715ES]之兩面浸漬於有機酸系蝕刻劑（Mecc (股）製， CZ8 100)中，對銅表面進行粗糙化處理。 (2 )接著薄膜之層合 以實施例及比較例作成之接著薄膜，使用批式真空加 壓層合機MVLP-500 C名機（股）製商品名），層合在層 合板兩面上。層合係藉由在30秒內減壓至氣壓成爲13hPa 以下，隨後於30秒內，以100°C、壓力0.74MPa加壓而 進行。 (3 )樹脂組成物之硬化 自經層合之接著薄膜剝離PET薄膜，在180 °C、30分 鐘之硬化條件使樹脂組成物硬化。 (4 )粗糙化處理 層合板浸漬於膨潤液之曰本 Atotech (股）之含有二 乙二醇單丁基醚之Sering Dip · SecurGund P中，接著浸 漬於粗糖化液之日本 Atotech (股）之 Concentrate· -27- 200923007200923007 As a flaky fiber base material composed of fibers, a fiber such as a woven fabric or an amide fiber can be used as a fiber for a prepreg. In the hot melt method, the resin is not dissolved in an organic solvent, and is applied to a coated paper having good releasability with a resin, and is coated on a layered fibrous substrate or directly by a dye spinner. Etc., the method of prepreg. Further, in the solvent method, similarly to the adhesive film, the fibrous base material may be immersed in a tree obtained by dissolving the resin in an organic solvent, and the resin varnish may be impregnated into the flaky fibrous base material, followed by drying. Next, a method of manufacturing the multilayered board of the present invention using the prepreg of the present invention will be described. On the circuit board, a piece of B of the present invention or a plurality of sheets as needed is superposed, and the release film is sandwiched between the release film and the right side under pressure. The pressure is preferably from 5 to 40 kgf/cm 2 104 to 3 92 x 10 4 N/m 2 ), preferably at a temperature of from 120 to 200 ° C, and is formed in a range of from 20 to 100 minutes. Further, after the film is laminated on the circuit board by the same method as the film, the film can be formed by heat curing. Subsequently, in the same manner as described above, the prepreg surface after curing is roughened by an oxidizing agent, and then a conductor layer is formed by electroplating to produce a multilayer printed board. The invention is described in more detail below using the examples and comparative examples, and the invention should not be construed as being limited thereto. In addition, in the following description, "meaning "mass portion". <Example 1> Glass ί Γ Γ 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 制造 1 1 1 1 1 1 i i i i i i i i i i i i i i i i i i i i i i i i i i -23- 200923007 30 parts of liquid double-type A epoxy resin (epoxy equivalent 丨80, "EPicote 828EL" made by Nippon Epoxy Co., Ltd.) and 30 parts of biphenyl type epoxy resin (epoxy equivalent 291' Nippon Chemical Co., Ltd. "NC3000H") is heated and dissolved in 15 parts of methyl ethyl ketone (hereinafter referred to as "MEK") and 15 parts of cyclohexanone while stirring, in which 'mix 1 part of naphthalene A phenolic curing agent ("SN48 5", a phenolic hydroxyl equivalent of 215) made by Dongdu Chemical Co., Ltd., a 50% solids MEK solution, and 0.1 part of a hardening catalyst ("4E4MZ" manufactured by Shikoku Chemical Industry Co., Ltd." ), 70 parts of spherical cerium oxide (average particle size 0.5μπι, "SO-C2" treated by amine sands, made by Admatechs), 20 parts of polyvinyl butyral resin solution (glass transition temperature 105 °C) , Sekisui Chemical Industry Co., Ltd. "KS-1" solids 15% ethanol and toluene 1:1 solution), 20 parts phenoxy resin ( A molecular weight of 3 8,000, "YX6954" made by Japan Epoxy Resin Co., Ltd., a 1:1 solution of MEK and cyclohexanone having a nonvolatile content of 30% by mass, and 8 parts of a phosphorus-containing benzoic acid represented by the formula (1) A sulphide (a product of the Showa Polymer Co., Ltd.: ^?-Β Ο Z 0 6, a solid solution of 65% dioxane), which is uniformly dispersed by a high-speed rotary mixer to prepare a resin varnish. The dye spin coater is coated on polyethylene terephthalate (thickness 38 μm) so that the thickness of the dried resin becomes 40 μm, and dried at 80 to 120 ° C (average 1 ° C) for 6 minutes (residue The amount of the solvent was about 2% by mass. Then, a polypropylene film having a thickness of 15 μm was attached to the surface of the resin composition while being wound into a roll shape, and the roll-shaped film was cut into a width of 507 mm, thereby obtaining a size of 5 07 mm x 3 3 6 mm. Sheet-like film. -24- 200923007 &lt;Example 2 &gt; 3 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 18 〇, "Epicote 828EL" manufactured by Nippon Epoxy Co., Ltd.) and 30 Biphenyl type epoxy resin (epoxy equivalent 291, "Nippon Chemical Co., Ltd." "NC3000H") at 1 5 The MEK and 15 parts of cyclohexanone are heated and dissolved while stirring, and 80 parts of a naphthol-based hardener ("SN4 85" manufactured by Tohto Kasei Co., Ltd., phenolic hydroxyl equivalent 2 1 5 ) is mixed therein. 50% MEK solution, 15 parts active ester hardener (EXB945 1 by Dainippon Ink Chemical Industry Co., Ltd., active base equivalent 223, solid content is 65 mass% in toluene), 0.1 part Hardening catalyst ("4 E 4Μ Z" made by Shikoku Chemical Industry Co., Ltd.), 70 parts of spherical cerium oxide (average particle size 0 · 5 μιη, "SO-C2" treated by amine brothel" Admatechs (Stock)), 20 parts of polyvinyl butyral resin solution (glass transition temperature 1 〇 5 °C 'Hydrochemicals of "KS-1" made by Sekisui Chemical Industry Co., Ltd.) 15% ethanol and toluene 1:1 Solution), 20 parts of phenoxy resin (molecular weight 3 8,000, "YX6954" made by Nippon Epoxy Resin Co., Ltd. '30% by mass of MEK and cyclohexanone 1: 1 solution), 15 parts (1) Representing the peculiar and spiroazine (HF_B〇Z06, manufactured by Showa Polymer Co., Ltd., 65% solid solution of dioxane), The high-speed rotary mixer is uniformly dispersed to make a tree varnish. Then, using this resin varnish, the following film was obtained in exactly the same manner as in Example 1. &lt;Comparative Example 1 &gt; In the resin varnish described in Example ί, except that 8 parts of phosphorus-containing benzene-25-200923007 and oxazide (HF-BOZ06 manufactured by Showa Polymer Co., Ltd.) were added, the solid content was 65%. The rest is identical except for the dioxane solution, and a film is obtained. &lt;Comparative Example 2 &gt; 30 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180 'Epicote 82 8EL made from Nippon Epoxy Co., Ltd.) and 30 parts of phosphorus-containing epoxy resin (epoxy equivalent) 3 06, "Tosei Chemicals Co., Ltd." "FX289") is heated and dissolved in 15 parts of MEK and 15 parts of cyclohexanone while stirring. In the case of 'mixing one part of the naphthol-based hardener ("SN485" made by Dongdu Chemical Co., Ltd., phenolic hydroxyl equivalent 215), the solid content of 50% of MEK solution, and the "hardening catalyst" (four countries) Chemical Industry Co., Ltd. '2E4MZ'), 70 parts of spherical oxidized sand (average particle size 〇. 5 μ m 'SO-C2 treated by amine sand yard, made by Admatechs), 20 parts Ethylene butyral resin solution (glass transition temperature 105. (:, KS-1 made by Sekisui Chemical Co., Ltd.): 15% ethanol and toluene 1:1 solution), 20 parts of phenoxy resin ( The molecular weight is 38,000, "YX6954" made by Japan Epoxy Resin Co., Ltd., and the non-volatile content of MEK and cyclohexanone 1.1 solution) is uniformly dispersed in a high-speed rotary mixer to produce a resin varnish. The resin varnish was obtained in the same manner as in Example 1. [Comparative Example 3 &gt; In the resin varnish described in Example 1, except for 8 parts of phosphorus-containing benzoxazine (HF-based product of Showa Polymer Co., Ltd.) BOZ06, 65% solid solution of methane, changed to 8 parts of phosphorus-based flame retardant (Sanguang) 2HCA_ -26- 200923007 HQ-HS) "The rest are identical" to obtain the adhesive film. <Modulation of peel strength and Ra値 measurement sample> (1) Underlayer treatment of laminate to form glass cloth of inner layer circuit The two sides of the substrate epoxy resin double-sided copper-clad laminate [copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Co., Ltd. R5 715ES] were immersed in an organic acid etchant (Mecc (manufactured by Mecc), CZ8 100) The copper surface was roughened. (2) The film was laminated with the film of the example and the comparative example, and the batch type vacuum pressure laminator MVLP-500 C machine was used. Laminated on both sides of the laminate. The lamination system was carried out by depressurizing to a gas pressure of 13 hPa or less in 30 seconds, followed by pressurization at 100 ° C and a pressure of 0.74 MPa in 30 seconds. (3) Curing of the resin composition The PET film was peeled off from the film which was laminated, and the resin composition was cured at 180 ° C for 30 minutes. (4) The roughened laminate is immersed in a swellable liquid of Atotech (s), Sering Dip · SecurGund P containing diethylene glycol monobutyl ether, and then immersed in Atotech (Japan) of crude saccharification solution. Concentrate· -27- 200923007

Compact P ( KMn04 : 60g/L，NaOH : 4 0 g/L 之水溶液）中 ，最後於中和液之日本 Atotech (股）之 Reduction Solution. SecurGund P中於40°C浸漬5分鐘。粗糖化條 件：於膨潤液中60°C浸漬5分鐘，於粗糙化液中8(TC浸漬 20分鐘。對該粗糙化處理後之層合板，進行表面粗糙度（ Ra値）測定。 (5 )依據半加成方法之電鍍 爲在絕緣層表面形成電路，將層合板浸漬於含有 PdCl2之無電解電鍍用溶液中，接著浸漬於無電解鍍銅液 中。於1 5 0 °C加熱3 0分鐘進行退火處理後，形成蝕刻阻劑 ，藉由蝕刻形成圖型後，進行硫酸銅電解電鍍，形成 30±5μιη厚之導體層。接著，於18(TC進行退火處理60分 鐘。對此層合板測定鍍銅之剝離強度。 &lt;電鍍導體層剝離強度（剝離強度）之測定&gt; 於層合板之導體層上’切成寬l〇mm '長100mm之部 分，剝離其一端並以捏具夾住’在室溫下’以50mm/分鐘 之速度，測定對於層合板略垂直方向剝離3 5mm時之荷重 &lt;粗糙化後表面粗糙度（Ra値）之測定&gt; 使用非接觸型表面粗糙度計（Veeco儀器公司製 WYKO NT3 3 00 )，自藉由VSI接觸模式' 50倍透鏡以 -28- 200923007 1 2 1 μ m x 9 2 μ m爲測定範圍所得之數値求得R a値。又藉由求 得1 〇點平均粗糙度而測定。 &lt;難燃性試驗用樣品之調製&gt; (1 )層合板之底層處理 於玻璃布基材環氧樹脂層合板[銅箔蝕刻除之產品， 基板厚度〇.3mm，松下電工（股）製R5 715ES]之兩面上 ，將實施例及比較例作成之接著薄膜，使用批式真空加壓 層合機MVLP-5 00 (名機（股）製商品名），層合於層合 板之兩面上。層合係於30秒內減壓至氣壓爲13 hPa以下 ，之後於3 0秒內，於1 〇 (TC、壓力〇. 74Mpa進行壓著。自 經層合之接著薄膜剝離PET薄膜後，於其上以相同條件進 而層合2次該相同接著薄膜。 (2 )樹脂組成物之硬化 於最後自層合之接著膜剝離PET薄膜，以180°C、90 分鐘之硬化條件使樹脂組成物硬化。其後，切斷成 1 2 Jmm X 127mm之尺寸作爲UL難燃性試驗用，其端面以 砂紙（最初爲#1200，接著使用#2800)予以硏磨，於基材 厚度0.3 mm單面上層合絕緣層120 μιη製作燃燒性試驗用 試驗片。隨後’依據UL耐火性試驗規格，進行94V0或 9 4 V 1之評價。 使用以實施例及比較例所得之接著薄膜之評價樣品之 -29- 200923007 電鑛導體層之剝離強度及粗糙化後之表面粗糙度（Ra値 )結果記載於表1。如由表1所了解，本發明中使用含隣 苯并噁嗪化合物之實施例之評價樣品，爲低粗糙度且高剝 離強度’難燃性爲V0而爲優良。又，於不使用含磷苯并 噁嗪化合物之比較例1之情況，獲得雖剝離強度較高，但 難燃性變差’粗糙度變大之結果。再者，替代本發明中之 含磷苯并噁嗪化合物而使用其他含磷化合物之比較例2及 3之情況，獲得雖剝離強度較高，但爲獲得如此高的剝離 強度，粗糙度應變大之結果。 表1 材料 實施例1 實施例2 比較例1 比較例2 比較例3 剝離強度(kgf/cm) 0.73 0.61 0.71 0.82 0.72 表面粗糙度(nm) 460 380 530 650 550 難燃性 V0 V0 VI V0 V0 [產業上之利用可能性] 本發明之樹脂組成物，於由該樹脂組成物所調製之接 著薄膜或預浸片可適當使用於作爲多層印刷電路板，尤其 是以（built-up )方式製造之多層印刷電路板之層間絕緣 材料。 本申請案係以於日本申請之特願2007-245 8 0 1作爲基 礎，其內容全部包含於本說明書中供參考。 -30-In Compact P (KMn04: 60 g/L, NaOH: 40 g/L aqueous solution), it was finally immersed in a reduction solution of Japan Atotech (Stock) in Solution Solution. SecurGund P at 40 ° C for 5 minutes. The conditions of the crude saccharification were immersed in a swelling liquid at 60 ° C for 5 minutes, and immersed in a roughening solution for 8 minutes (TC immersion for 20 minutes. The surface roughness (Ra 値) of the laminate after the roughening treatment was measured. (5) According to the semi-additive method, a circuit is formed on the surface of the insulating layer, the laminate is immersed in a solution for electroless plating containing PdCl 2 , and then immersed in an electroless copper plating solution, and heated at 150 ° C for 30 minutes. After the annealing treatment, an etching resist was formed, and a pattern was formed by etching, and then copper sulfate electroplating was performed to form a conductor layer having a thickness of 30 ± 5 μm, followed by annealing at 18 (TC for 60 minutes). Peeling strength of copper plating. <Measurement of peeling strength (peeling strength) of electroplated conductor layer> On a conductor layer of a laminate, 'cut into a width of 100 mm long, and peel off one end and pinch it with a jig 'Measurement at a temperature of 50 mm/min at a temperature of 50 mm/min for the peeling of the laminate in a direction slightly perpendicular to the vertical direction of 3 5 mm&lt;Measurement of surface roughness (Ra値) after roughening&gt; Using a non-contact type surface roughness meter (Veeco Instruments WYKO NT3 3 00 ), R 値 is obtained from the number obtained by the VSI contact mode '50 times lens with -28- 200923007 1 2 1 μ mx 9 2 μ m for the measurement range. Also by obtaining 1 〇 <Measurement of point average roughness. &lt;Preparation of sample for flame retardancy test&gt; (1) Underlayer treatment of laminate board on glass cloth substrate epoxy resin laminate [product of copper foil etching, substrate thickness 〇.3 mm On both sides of R5 715ES, manufactured by Matsushita Electric Works Co., Ltd., the film and the comparative example were used as the film, and the batch vacuum pressure laminator MVLP-5 00 (trade name of the brand) was used. The laminate is bonded to both sides of the laminate. The laminate is decompressed to a pressure of 13 hPa or less within 30 seconds, and then pressed at 1 Torr (TC, pressure 〇. 74 MPa) in 30 seconds. After the film was peeled off from the PET film, the same adhesive film was further laminated twice under the same conditions. (2) The resin composition was cured at the final self-laminated adhesive film to peel the PET film at 180 ° C for 90 minutes. The hardening condition hardens the resin composition. Thereafter, it is cut into a size of 1 2 Jmm X 127 mm as UL flame retardancy. For the inspection, the end face was honed with sandpaper (originally #1200, then #2800), and a test piece for the flammability test was prepared by laminating an insulating layer of 120 μm on a single substrate thickness of 0.3 mm. Test specifications, evaluation of 94 V0 or 9 4 V 1. Using the evaluation samples of the adhesive films obtained in the examples and comparative examples, the peel strength of the electric conductor layer and the surface roughness after roughening (Ra 値 -29-200923007) The results are shown in Table 1. As is understood from Table 1, in the present invention, the evaluation sample of the example containing the o-benzoxazine compound was excellent in low roughness and high peel strength & flame retardancy V0. Further, in the case of Comparative Example 1 in which the phosphorus-containing benzoxazine compound was not used, the result was that the peel strength was high, but the flame retardancy was deteriorated, and the roughness was increased. Further, in the case of Comparative Examples 2 and 3 in which other phosphorus-containing compounds were used instead of the phosphorus-containing benzoxazine compound in the present invention, the peel strength was obtained, but the peel strength was obtained, and the roughness strain was large. The result. Table 1 Material Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Peel strength (kgf/cm) 0.73 0.61 0.71 0.82 0.72 Surface roughness (nm) 460 380 530 650 550 Flame retardancy V0 V0 VI V0 V0 [ Industrial Applicability] The resin composition of the present invention can be suitably used as a multilayer printed circuit board, especially in a built-up manner, in an adhesive film or prepreg prepared by the resin composition. Interlayer insulating material for multilayer printed circuit boards. The present application is based on Japanese Patent Application No. 2007-245 801, the entire contents of which are incorporated herein by reference. -30-

Claims (1)

200923007 十、申請專利範圍 1-一種環氧樹脂組成物，其特徵爲含有（A)環氧樹 脂、（B)環氧硬化劑、（C)苯氧樹脂及/或聚乙烯縮醛 樹脂以及（D )含有磷之苯并噁嗪化合物。 2.如申請專利範圍第1項之環氧樹脂組成物，其中該 含磷之苯并噁嗪化合物爲以下式（1 )表示之含磷苯并噁 嗪化合物： [化1]200923007 X. Patent Application No. 1 - An epoxy resin composition characterized by containing (A) epoxy resin, (B) epoxy hardener, (C) phenoxy resin and/or polyvinyl acetal resin and D) a benzoxazine compound containing phosphorus. 2. The epoxy resin composition according to claim 1, wherein the phosphorus-containing benzoxazine compound is a phosphorus-containing benzoxazine compound represented by the following formula (1): [Chemical Formula 1] 3 ·如申請專利範圍第1或2項之環氧樹脂組成物，其 中該環氧硬化劑爲選自酚系硬化劑、萘酚系硬化劑及活性 酯系硬化劑之1種以上之環氧硬化劑。 4 ·如申請專利範圍第1至3項中任一項之環氧樹脂組 成物，其中以該環氧樹脂組成物之不揮發成分作爲丨〇〇質 量％時，成分（A)之含量爲10〜50質量％，成分（C)之 含量爲2〜2〇質量％，以及成分（D)之含量爲2〜20質量％ ’且環氧硬化劑之反應基相對於環氧樹脂組成物中存在之 1個環氧基之比例爲1 : 0.5〜1 : 1 . 1。 5 ·如申請專利範圍第1至4項中任一項之環氧樹脂組 成物，其進而含有無機塡充劑。 6.如申請專利範圍第5項之環氧樹脂組成物，其中以 -31 - 200923007 該環氧樹脂組成物之不揮發成分作爲1 0 0質量％時，該無 機塡充劑之含量爲10〜60質量％。 7 · —種接著薄膜’其特徵係於支撐薄膜上形成有申請 專利範圍第1至6項中任一項之環氧樹脂組成物之層而成 者。 8 · —種預浸片，其特徵係於由纖維所構成薄片狀纖維 基材中含浸有申請專利範圍第1至6項中任一項之環氧樹 脂組成物而成者。 9. 一種多層印刷電路板，其特徵係形成有由申請專利 範圍第1至6項中任一項之環氧樹脂組成物的硬化物所成 之絕緣層者。 10. —種多層印刷電路板之製造方法，其具有在內層 電路基板上形成絕緣層之步驟以及在該絕緣層上形成導體 層之步驟者，其特徵爲該絕緣層係使申請專利範圍第1至 6項中任一項之環氧樹脂組成物加以熱硬化所形成，該導 體層係藉由於該絕緣層表面經粗糙化處理之粗糙化面上進 行電鏟而形成。 1 1 . 一種多層印刷電路板之製造方法，其具有在內層 電路基板上形成絕緣層之步驟以及在該絕緣層上形成導體 層之步驟者，其特徵爲具有絕緣層形成步驟、該絕緣層之 粗面化步驟及對該粗面進行電鍍之步驟；該絕緣層形成步 驟係具有於內層電路基板上層合申請專利範圍第7項之支 持薄膜上之形成層之接著薄膜之步驟以及使環氧樹脂組成 物熱硬化之步驟。 -32- 200923007 I2·—種多層印刷電路板之製造方法，其具有在內層 電路基板上形成絕緣層之步驟以及在該絕緣層上形成導體 層之步驟者，其特徵爲該絕緣層係在內層電路基板上層合 申請專利範圍第8項之預浸片，使環氧樹脂組成物加以熱 硬化所形成，該導體層係藉由於該絕緣層表面經粗糙化處 理之粗糙化面上進行電鍍而形成。 1 3 ·如申請專利範圍第1 0至1 2項中任一項之多層印 刷電路板之製造方法，其中該粗糙化處理係使用鹼性過錳 酸溶液而進行。 -33- 200923007 七 指定代表圖： (一） 、本案指定代表圖為：無 (二） 、本代表圖之元件代表符號簡單說明：無 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無3. The epoxy resin composition according to claim 1 or 2, wherein the epoxy curing agent is one or more epoxy resins selected from the group consisting of a phenolic curing agent, a naphthol curing agent, and an active ester curing agent. hardener. The epoxy resin composition according to any one of claims 1 to 3, wherein the content of the component (A) is 10 when the nonvolatile content of the epoxy resin composition is 丨〇〇% by mass. ～50% by mass, the content of the component (C) is 2 to 2% by mass, and the content of the component (D) is 2 to 20% by mass 'and the reactive group of the epoxy hardener is present in the epoxy resin composition The ratio of one epoxy group is 1:0.5~1:1.1. The epoxy resin composition according to any one of claims 1 to 4, which further contains an inorganic chelating agent. 6. The epoxy resin composition according to claim 5, wherein the content of the inorganic chelating agent is 10% when the non-volatile component of the epoxy resin composition is -31 - 200923007 as 100% by mass. 60% by mass. A contiguous film is characterized in that a layer of the epoxy resin composition of any one of claims 1 to 6 is formed on the support film. A type of prepreg is characterized in that the sheet-like fibrous base material composed of fibers is impregnated with the epoxy resin composition according to any one of claims 1 to 6. A multilayer printed circuit board characterized by being formed of an insulating layer formed of a cured product of the epoxy resin composition according to any one of claims 1 to 6. 10. A method of manufacturing a multilayer printed circuit board, comprising the steps of forming an insulating layer on an inner layer circuit substrate and forming a conductor layer on the insulating layer, wherein the insulating layer is in a patent application scope The epoxy resin composition according to any one of items 1 to 6 is formed by thermal hardening, and the conductor layer is formed by performing a shovel on the roughened surface of the surface of the insulating layer which has been roughened. 1 1. A method of manufacturing a multilayer printed circuit board, comprising the steps of forming an insulating layer on an inner layer circuit substrate and forming a conductor layer on the insulating layer, characterized by having an insulating layer forming step, the insulating layer a roughening step and a step of plating the rough surface; the insulating layer forming step is a step of laminating a film forming a layer on the support film of the seventh aspect of the patent application on the inner circuit substrate and the ring The step of thermally hardening the oxy-resin composition. -32-200923007 I2. A method of manufacturing a multilayer printed circuit board having the steps of forming an insulating layer on an inner layer circuit substrate and forming a conductor layer on the insulating layer, wherein the insulating layer is attached The prepreg of the eighth aspect of the patent application is laminated on the inner circuit board to form an epoxy resin composition which is thermally hardened by plating on the roughened surface of the surface of the insulating layer by roughening treatment. And formed. The method of producing a multilayer printed circuit board according to any one of claims 10 to 12, wherein the roughening treatment is carried out using an alkaline permanganic acid solution. -33- 200923007 Seven designated representatives: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description: No. 8. If there is a chemical formula in this case, please reveal the characteristics that can best show the invention. Chemical formula: none
TW097136127A 2007-09-21 2008-09-19 Epoxy resin composition TWI433887B (en)

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