TW200400242A - Adhesive film and prepreg - Google Patents

Adhesive film and prepreg Download PDF

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Publication number
TW200400242A
TW200400242A TW092114159A TW92114159A TW200400242A TW 200400242 A TW200400242 A TW 200400242A TW 092114159 A TW092114159 A TW 092114159A TW 92114159 A TW92114159 A TW 92114159A TW 200400242 A TW200400242 A TW 200400242A
Authority
TW
Taiwan
Prior art keywords
epoxy resin
resin composition
component
circuit board
film
Prior art date
Application number
TW092114159A
Other languages
Chinese (zh)
Inventor
Shigeo Nakamura
Original Assignee
Ajinomoto Kk
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ajinomoto Kk filed Critical Ajinomoto Kk
Publication of TW200400242A publication Critical patent/TW200400242A/en

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2461/00—Presence of condensation polymers of aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
    • 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
    • H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer
    • H05K3/4676—Single layer compositions

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Adhesive Tapes (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

This invention provides an adhesive film characterized by comprising a substrate film and formed thereon a layer of an epoxy resin composition comprising the following ingredients (A) to (C): (A) an aromatic epoxy resin having two or more epoxy groups per molecule, (B) a cyanate compound having two or more cyanato groups per molecule, and (C) a phenoxy resin having a weight-average molecular weight of 5,000 to 100,000; and a prepreg characterized by comprising an epoxy resin composition comprising the ingredients (A) to (C) that is infiltrated in a sheet-form reinforcing base made of fibers.

Description

200400242 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關做爲電氣絕緣材料有用之黏接用薄膜及 預漬體，特別是做爲多層印刷電路板之層間絕緣材料有用 之黏接用薄膜及預漬體。本發明又有關藉由該黏接用薄膜 及該預漬體後形成絕緣層之多層印刷電路板，該多層印刷 電路板之製造方法。 · 【先前技術】 近年來，電子機器、通訊器等所使用之印刷電路板中 ，被強烈要求演算處理速度之高速化、配線之高密度化。此 同時，做爲多層印刷電路板之製造方法者，使有機絕緣層 交互層合於電路基板導體層之積累方式的製造技術被重視 。做爲目前以積累方式所使用之絕緣樹脂者主要使用組 合具有活化氫於芳香族系環氧樹脂之硬化劑（如：苯酚系 硬化劑、胺系硬化劑、羧酸系硬化劑）者。以此等硬化劑 所硬化取得之硬化物其物性面均衡雖良好，惟，藉由環氧 基與活化氫反應後產生極性高之羥基後，將導致降低耐濕 性、誘電率、誘電正切等電氣特性之負面影響。特別是於 高周波領域所使用之多層印刷電路板中被要求低誘電正切 之絕緣材料，而，以先行環氧系樹脂做爲主成份之絕緣材 料時其誘電正切（1GHz、23 °C )之値呈0 03〜0 02者爲極 限。 另外’具有熱硬化性氰氧基之氰酸酯化合物爲具有良 -4- (2) (2)200400242 好誘電特性Z硬化物乃自古即爲公知者。惟，氰氧基藉由 熱硬化後形成S -三嗪環之反應務必於2 3 0 °C 2小時以上之 高溫下進行較長時間之硬化’因此，以氰酸酯化合物做爲 一般F R 4基板C玻璃轉移點1 3 5 °C )用之絕緣材料使用極 爲困難者。 做爲降低氰酸酯化合物硬化溫度之方法者公知者係使 氰酸酯化合物倂用環氧樹脂後，使用硬化觸媒進行硬化之 方法者。此法中係環氧樹脂之環氧基與氰酸酯化合物之氰 氧基反應後形成噁唑啉環之反應爲主反應者，熱硬化後出 現損及誘電正切之羥基，抑制損及誘電正切之氰氧基殘存 做爲氰酸酯化合物之硬化觸媒者如：苯酚化合物與有 機金屬化合物爲公知者。惟，以苯酚化合物做爲硬化觸媒 使用時，於黏接用薄膜、預漬體之製造時進行加熱乾燥步 驟後，其樹脂組成物之保存安定性（適用期）出現明顯受 損之問題。又，使用有機金屬化合物之系中，熱硬化時之 凝膠時間大大受制於數百ppm微量觸媒添加量，因此不易 控制凝膠時間，而不適於工業生產者。 由以上，本發明以提供一種利用環氧樹脂與氰酸酯化 合物之系，發揮良好硬化物電氣特性與良好硬化特性，且 ，適用期亦佳之適於多層印刷電路板工業生產之黏接用薄 膜及預漬體爲目的者。 【發明內容】 -5- (3) (3)200400242 本發明者爲解決該課題而進行精密硏討之結果發現藉 由特定之環氧樹脂，特定之氰酸酯化合物及特定苯氧基樹 脂所構成之黏接用薄膜及預漬體後可解決該課題，進而完 成本發明。亦即，本發明爲含有以下內容者。 [1 ]含下記成份（A )〜（c )之環氧樹脂組成物被層形 成於支撐體爲其特徵之黏接用薄膜， (A) 1分子中具有2以上環氧基之芳香族系環氧樹 脂， (B ) 1分子中具有2以上氰氧基之芳香族系氰酸酯 化合物，以及 (C)重量平均分子量爲5 000〜100，000之苯氧基樹脂 〇 [2]成份（C)之苯氧基樹脂爲具有聯苯基骨架之苯氧 基樹脂之該[1 ]之黏接用薄膜。 [3 ]環氧樹脂組成物之加熱硬化後誘電正切於測定周 波數1GHz及溫度 23 °C之條件下爲 0 015以下之該 [1 ]〜[2 ]之黏接用薄膜。 [4]環氧樹脂組成物中成份（A)之芳香族系環氧樹脂 之環氧基與成份（B )之芳香族系氰酸酯化合物之氰氧基 比例爲1 : 0 5〜1 : 3者，針對成份（A )與成份（B )總量 100重量份時，成份（C )之苯氧基樹脂爲3〜40重量份之該 [1 ]〜[3 ]之黏接用薄膜。 [5 ]藉由該[1 ]〜[4 ]所載黏接用薄膜後形成絕緣層之多 層印刷電路板。 -6- (4) (4)200400242 [6] 該[1]〜[4]之黏接用薄膜於加壓及加熱條件下層壓 料於電路基板後，必要時剝離支撐薄膜，使層壓塑料於電 路基板之環氧樹脂組成物進行加熱硬化後形成絕緣層後， 未剝離支撐薄膜時，必要時將其剝離後，再於必要時以氧 化劑粗化該絕緣層表面，藉由電鍍導體層後含形成之步驟 爲其特徵之多層印刷電路板之製造方法。 [7] 藉由該[6]之製造方法取得之多層印刷電路板。 [8] 含下記成份（A)〜（C )之環氧樹脂組成物浸漬於 由纖維所成之薄片狀補強基材中爲其特徵之預漬體， (A) 1分子中具有2以上環氧基芳香族系環氧樹脂 (B ) 1分子中具有2以上氰氧基芳香族系氰酸酯化 合物，以及 (C)重量平均分子量爲5000〜100，〇〇〇之苯氧基樹脂 〇 [9] 成份（C )之苯氧基樹脂爲具有聯苯基骨架之苯氧 基樹脂之該[8 ]之預漬體。 [1 0]環氧樹脂組成物之加熱硬化後比誘電率於測定周 波數1GHz及溫度 23 °C之條件下爲 0 015以下之該 [8]〜[9]之預漬體。 [1 1 ]環氧樹脂組成物中成份（A )之芳香族環氧樹脂 之環氧基與成份（B )芳香族系氰酸酯化合物之氰氧基比 例爲1 : 〇 5〜1 : 3者，針對100重量份之成份（A )與成 份（B )總量，其成份（C )之苯氧基樹脂配合3〜4 0 S量 (5) (5)200400242 份之該[8]〜[10]之預漬體。 [12]藉由該[8]〜[Π]之預漬體形成絕緣層之多層印刷 電路板。 [1 3 ]該[8 ]〜[1 []之預漬體於加壓及加熱條件下層壓塑 料於電路基板及硬化後形成絕緣層後，必要時，以氧化劑 粗化該絕緣層表面，藉由電鍍導體層所含之形成步驟爲其 特徵之多層印刷電路板的製造方法。 [1 4 ]藉由該[1 3 ]之製造方法取得之多層印刷電路板。 [發明實施之形態] 以下，進行本發明詳細說明。 本發明中成份（A )之「1分子中具2以上環氧基之 ~方香族系環氧基樹脂」係指1分子中具有2以上環氧基， 且’分子中具有芳香環骨架之環氧樹脂者。做爲1分子中 具有2以上環氧基之芳香族系環氧樹脂之理想例者如：雙 酚A型環氧樹脂、雙酚ρ型環氧樹脂、雙酚s型環氧樹 月曰、本酚漆用酚醛型環氧樹脂、烷基苯酚漆用酚醛型環氧 樹脂、聯苯型環氧樹脂、二環戊二烯型環氧基樹脂、具苯 酸類與苯酚性羥基之芳香族醛相互之縮合物環氧化物、萘 型環氧樹脂、三縮水甘油基三聚異氰酸酯，更有此等溴化 壌氧樹脂、磷改性環氧樹脂等例者。此等環氧樹脂可分別 單獨使用，亦可組合2種以上使用之。 本發明中成份（B)之「1分子中具有2以上氰氧基 <芳曰族系氰酸酯化合物」係指1分子中具有2以上气氧 (6) (6)200400242 基’且，分子中具有芳香環骨架之氰酸酯化合物者，做爲 理想之1分子中具2以上氰氧基之芳香族系氰酸酯化合物 之例者如：雙酚A二氰酸酯、聚苯酚氰酸酯（低聚（3 -亞 甲基-1，5 -二苯氰酸酯）、4，4’ -亞甲基雙（2，6 -二甲基 苯基氰酸酯）、4，4'-亞乙基二苯基二氰酸酯、六氟雙酚 A二氰酸酯、此等部份被三嗪化之預聚體等例。此等氰酸 酯化合物可分別單獨使用，亦可組合2種以上使用之。 環氧樹脂組成物中成份（A )之1分子中所存在之環 氧基與成份（B )之1分子中所存在氰氧基比例爲1 : 0 5〜1 : 3者宜。若不在此範圍者則硬化後藉由所殘留之未 反應環氧基或氰氧基無法取得充份低的誘電正切値。另外 ，環氧樹脂組成物中具有成份（A )以外之環氧基化合物 ，成份（B )以外之氰氧基化合物時，此等成份亦包含環 氧基與氰氧基比例爲該範圍內者。亦即，存在於環氧樹脂 組成物中環氧基與氰氧基比例以1 : 0 5〜1 ·· 3者宜。 以下，針對本發明成份（C)之「重量平均分子量爲 5 0 00〜100，〇〇〇之苯氧基樹脂」進行說明。 苯氧基樹脂係由2官能環氧樹脂與雙酚化合物之反應 生成物所成之聚合物者，存在於分子中之羥基顯示促進環 氧基與氰氧基之硬化作用，因此，被認爲於較低之硬化溫 度下可有效發揮硬化物性（耐熱性、低誘電正切等）。氰 酸酯化合物與環氧樹脂所成之樹脂組成物中，環氧樹脂具 羥基時雖出現促進硬化作用，惟，此羥基有惡化樹脂組成物 之適用期乃公知者。另外，本發明者於成份（A)及成3 ( (7) (7)200400242 B)中倂用高分子苯氧基樹脂成份（C )後，則無惡化環氧 樹脂組成物之適用期，且出現發揮良好硬化物性者。藉由 添加成份（C )之苯氧基樹脂後，可提昇環氧樹脂硬化物 氧化劑之粗化性，藉由電鍍亦可出現導體層形成。 做爲重量平均分子量爲5000〜100，000之苯氧基樹脂 的理想例者如：雙酚A型之Phenotot YP 50 (東都化成（ 股份）製）、E- 1 2 5 6 (日本環氧樹脂（股份）製）之外， 被溴化之苯氧樹脂之 Phenotot YP B4〇 (東都化成（股份 )製）等例。 做爲成份（C )者特別是具有聯苯骨架之重量平均分 子量爲5 000〜100，0 0 0之苯氧基樹脂具耐熱性、耐濕性及 促進硬化作用爲理想者。此苯氧基樹脂之具體例如：聯苯 型環氧樹脂（日本環氧樹脂（股份）製YX 4〇 00)與各種 雙酚化合物相互反應生成物所成之苯氧基樹脂者、YL 6742BH30 、 YL6835BH40 、 YL6953BΗ30 、 YL6954BH30 、 YL6974BH30 、 ΥΧ8100ΒΗ30 之例者。 此等苯氧樹脂可分別單獨使用，亦可組合2種以上 使用之。 重量平均分子量爲5000〜100，000之苯氧基樹脂可使 促進硬化作用之外，亦易於提昇黏接用薄膜及預漬體之活 動性之使用，同時亦可提昇硬化物之機械強度、活動性。 且’可藉由硬化物氧化劑之粗化。另外，當成份（C )樹 脂之重量平均分子量不足5 000時，則該效果將不足，反 之’超出1 00，〇〇〇則環氧樹脂及有機溶劑之溶解性將明 -10- (8) (8)200400242 顯降低，實際上使用不易。 有關成份（C)之樹脂配合量依其種類不同而異，一 般，針對i 00重量份之成份（A )環氧樹脂與成份（B ) 之氰酸酯化合物總量時，以配合3〜40重量份者宜。特別 以5〜2 5重量份爲更佳。當不足3重量份時，則樹脂組成 物之促進硬化作用將不足，樹脂組成物層壓塑料（層合） 於電路基板時，或熱硬化層壓塑料之樹脂組成物時，樹脂 流動性變得太大、絕緣層厚度呈不均。又，亦無法取得因 導體層形成之硬化物粗化性。反之，超出40重量份則苯氧 基樹脂之官能基存在過剩，而無法取得充份低的誘電正切値 ，更於電路基板使樹脂組成物層壓塑料時之流動性太低， 使得存在於電路基板之穿孔、通氣孔內樹脂塡充不能有效 進行。 本發明環氧樹脂組成物中此等成份（A )〜（C )之總 含量並未特別限定，一般當該環氧樹脂組成物爲1 00重量％ 時，以含有2 5重量％〜9 0重量％者宜。 本發明環氧樹脂組成物於必要時更縮短硬化時間爲目 的下，亦可添加先行環氧樹脂組成物與氰酸酯化合物倂用 之系做爲硬化觸媒使用之有機金屬化合物。先行之系中， 使用有機金屬化合物後，熱硬化時之凝膠時間受制於數百 ppm微量有機金屬化合物添加量而不易控制，而，本發明 環氧樹脂組成物中有機金屬化合物因具有補助硬化之功能 ，因此即使添加有機金屬觸媒時乃可易於控制凝膠時間， 可提供適於多層印刷電路板之工業生產的黏接用薄膜及預 -11 - (9) (9)200400242 漬體者。做爲此有機金屬化合物者如：銅（11 )乙醯丙酮 配位基等有機銅化合物、鋅（II )乙醯丙醒配位基等有機 鋅化合物、鈷（II )乙醯丙酮配位基、鈷（III )乙醯丙酮 配位基等有機鈷化合物例者。添加有機金屬化合物之添加 量一般針對（B)成份「i分子中具2以上之氰氧基芳香族 系氰酸酯化合物」換算金屬後以10〜500ppm者宜，較佳者 爲25〜200ppm。 鲁 本發明環氧樹脂組成物中，必要時，爲降低所形成絕 緣層之熱膨脹亦可添加無機塡充材。添加無機塡充材之添 加量依本發明環氧樹脂組成物之特性，所求機能而定，一 般當該環氧樹脂組成物爲100重量％時爲10〜75重量％配 合者宜，較佳者爲2 0〜6 5重量％。 做爲無機塡充材料者如：二氧化矽、氧化鋁、硫酸鋇 、滑石、粘土、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、鈦酸緦、鈦酸鈣 _ 、鈦酸鎂、鈦酸鉍、氧化鈦、锆酸鋇、锆酸鈣等例。特別以 二氧化矽爲佳。無機塡充材料其平均粒徑爲5 μιη以下者宜 。當平均粒徑超出5 μιη時，則形成電路圖案於導體層時不 易安定進行細圖案。又，無機塡充材料爲提昇耐濕性，以矽 烷偶合劑等表面處理劑進行表面處理者宜。 本發明環氧樹脂組成物中成份之外，在不阻擾本發明 效果範圍下，於必要時，更可使用其他熱硬化性樹脂、熱 可塑性樹脂、添加劑。做爲熱硬化性樹脂者如··做爲稀釋 劑之單官能環氧樹脂之外，脂環式多官能環氧樹脂、2膠 -12- (10) (10)200400242 改性環氧樹脂，做爲環氧樹脂用硬化劑之酸無水物系化合 物、欧段異氰酸酯樹脂、二甲苯樹脂、自由基產生劑與聚 合性樹脂等例。做爲熱塑性樹脂例者如：聚亞胺樹脂、聚 醯胺亞胺樹脂、聚醚亞胺樹脂、聚硕樹脂、聚醚硕樹脂、 聚二苯醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂 等例。做爲添加劑之例者如，聚矽氧粉末、尼龍粉末、氟 粉等有機塡充劑、有機改性樹潤土、聚氯醚樹脂等之增粘 劑、聚矽氧系、氟系、高分子系之消泡劑或矯正劑、咪唑 系、噻唑系、三唑系、矽烷偶合劑等密合性附與劑、酞青 、綠、碘、綠、二重氮黃、碳黑等之著色劑例者。 本發明環氧樹脂組成物可形成良好耐熱性及電氣特性 之硬化物。如：可形成滿足高周波領域所使用之印刷電路 板所求之誘電正切條件（如：於測定周波數1 GHZ及溫度 2 3 °C之條件下爲0 0 1 5以下）之硬化物者。 以下，針對本發明黏接用薄膜進行說明。 將該（A )〜（C )做爲必須成份之環氧樹脂組成物溶 於有機溶劑做成樹脂淸漆後，將此塗佈於支撐體之底層薄 膜（支撐薄膜）後，以熱風噴塗等方式藉由乾燥溶劑後， 可製造本發明黏接用薄膜。 做爲有機溶劑例者如：丙酮、丁酮、環己酮等酮類、 醋酸乙酯、醋酸丁酯、溶纖劑乙酸酯、丙二醇單甲醚乙酸酯 '卡必醇乙酸酯等醋酸酯類、溶纖劑、丁基卡必醇等卡必醇 類、甲苯、二甲苯等芳香族烴基類、二甲基甲醯胺、二甲 基乙醯胺N-甲基吡咯烷酮等例。有機溶劑亦可組合a種 -13- (11) (11)200400242 以上使用之。 該業者可藉由簡單實驗設定適當理想之乾燥條件。如 :可於80〜100 °C下以3〜10分鐘進行乾燥含有30〜60重 量％之有機溶劑的淸漆。殘存於環氧樹脂組成物之有機溶 劑量一般以1 〇重量7。以下爲宜，較佳者爲5重量％以下。 本發明黏接用薄膜其構成該黏接用薄膜之環氧樹脂組 成物層用於真空層壓塑料法時以具有適當熔解黏度特性者 宜。亦即，本發明黏接用薄膜於真空層壓塑料之溫度條件 (一般7 〇 °c〜14〇 °c )下進行軟化後，出現流動性、穿 孔、通氣孔存在時，於真空層壓塑料時以可同時一倂進行 往此孔塡充樹脂者宜。此熔解黏度特性被揭示於W〇 0 1 /97 5 82號公報，可依環氧樹脂組成物之動粘彈性率測定 所求出之溫度-熔解黏度曲線而決定之。測定開始溫度做 成6 〇 °C，於5 °C /分鐘之昇溫速度下加熱後測定熔解黏 度後’求出溫度-熔解黏度曲線時，第1表代表各溫度溶 解黏度之値爲滿足該特性之理想黏接用薄膜者。 -14- (12) 200400242200400242 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to an adhesive film and a pre-staining body which are useful as electrical insulation materials, especially useful as an interlayer insulation material of a multilayer printed circuit board. Use film and pre-stained body. The present invention also relates to a multilayer printed circuit board having an insulating layer formed by the adhesive film and the pre-stained body, and a method for manufacturing the multilayer printed circuit board. · [Previous technology] In recent years, in printed circuit boards used in electronic equipment, communicators, etc., there has been a strong demand for a higher speed of calculation processing speed and a higher density of wiring. At the same time, as a method of manufacturing a multilayer printed circuit board, the manufacturing method of an accumulation method in which an organic insulating layer is alternately laminated on a conductor layer of a circuit substrate is valued. As the insulating resins currently used in a cumulative manner, those who use a combination of hardeners with activated hydrogen in aromatic epoxy resins (such as phenol-based hardeners, amine-based hardeners, and carboxylic acid-based hardeners) are mainly used. Although the physical properties of the hardened material obtained by hardening with these hardeners are well balanced, the reaction with epoxy groups and activated hydrogen produces highly polar hydroxyl groups, which will result in reduced humidity resistance, electrical induction rate, and electrical tangent. Negative effects of electrical characteristics. Especially for multilayer printed circuit boards used in high-frequency fields, low-induced dielectric tangent insulation materials are required, and when an epoxy resin is used as the main component of the insulating material, the dielectric tangent (1GHz, 23 ° C) is one of The limit is 0 03 ~ 02. In addition, a cyanate ester compound having a thermosetting cyanooxy group has a good -4- (2) (2) 200400242. Good Z-curable materials have been known since ancient times. However, the reaction of the cyanooxy group to form an S-triazine ring after thermal hardening must be hardened at a high temperature of more than 2 hours for 2 hours. Therefore, cyanate compounds are generally used as FR 4 Substrate C glass transition point 1 3 5 ° C) It is extremely difficult to use the insulating material. A known method for lowering the curing temperature of a cyanate compound is a method in which a cyanate compound is mixed with an epoxy resin and then cured using a curing catalyst. In this method, the epoxy group reacts with the cyano group of the cyanate compound to form an oxazoline ring. The main reaction group is the hydroxyl group that damages the electromotive tangent after heat curing, and inhibits the damage and the electromotive tangent. Residual cyanooxy groups are known as hardening catalysts for cyanate compounds such as phenol compounds and organometallic compounds. However, when a phenol compound is used as a hardening catalyst, after the heat-drying step is performed during the production of the adhesive film and the pre-stained body, the storage stability (applicable period) of the resin composition is significantly impaired. Moreover, in the system using an organometallic compound, the gel time during heat curing is greatly restricted by the amount of a few hundred ppm of the catalyst added, so it is difficult to control the gel time, and it is not suitable for industrial producers. From the above, the present invention provides an adhesive film that is suitable for the industrial production of multilayer printed circuit boards by utilizing the system of epoxy resin and cyanate compound, which exhibits good electrical properties and good hardening properties of hardened materials, and has a good pot life. And pre-stained body for the purpose. [Summary of the Invention] -5- (3) (3) 200400242 As a result of an intensive study conducted by the present inventor to solve the problem, it was found that the specific epoxy resin, specific cyanate compound, and specific phenoxy resin were used. This problem can be solved by the adhesive film and the pre-stained body formed, and the present invention has been completed. That is, this invention contains the following. [1] The epoxy resin composition containing the following components (A) to (c) is formed on an adhesive film characterized by a support layer, (A) An aromatic system having 2 or more epoxy groups in one molecule Epoxy resin, (B) an aromatic cyanate compound having 2 or more cyanooxy groups in one molecule, and (C) a phenoxy resin having a weight average molecular weight of 5,000 to 100,000. [2] Component ( The phenoxy resin of C) is a film for bonding the [1] of the phenoxy resin having a biphenyl skeleton. [3] The induction tangent of the epoxy resin composition after heating and hardening is measured at a frequency of 1 GHz and a temperature of 23 ° C of 0 015 or less. The adhesive film of [1] to [2]. [4] The ratio of the epoxy group of the aromatic epoxy resin of the component (A) and the aromatic cyanate compound of the component (B) in the epoxy resin composition is 1: 0 5 to 1: For three, when the total amount of the component (A) and the component (B) is 100 parts by weight, the phenoxy resin of the component (C) is 3 to 40 parts by weight of the film for adhesion of [1] to [3]. [5] A multilayer printed circuit board having an insulating layer formed by the adhesive films carried in [1] to [4]. -6- (4) (4) 200400242 [6] After the adhesive film of [1] ~ [4] is laminated on the circuit board under pressure and heating conditions, if necessary, the support film is peeled off to make the laminated plastic After the epoxy resin composition of the circuit board is heated and hardened to form an insulating layer, when the supporting film is not peeled off, it is peeled off if necessary, and then the surface of the insulating layer is roughened with an oxidizing agent if necessary, and after the conductive layer is plated A method for manufacturing a multilayer printed circuit board including a forming step as a feature. [7] A multilayer printed circuit board obtained by the manufacturing method of [6]. [8] The epoxy resin composition containing the following components (A) to (C) is immersed in a sheet-shaped reinforcing substrate made of fibers, which is a characteristic pre-stained body, (A) has 2 or more rings in one molecule The oxyaromatic epoxy resin (B) has 2 or more cyanooxy aromatic cyanate compounds in one molecule, and (C) a phenoxy resin having a weight average molecular weight of 5000 to 100,000. 9] The phenoxy resin of the component (C) is a pre-stained body of the [8] of the phenoxy resin having a biphenyl skeleton. [1 0] The specific electric conductivity of the epoxy resin composition after heating and hardening is the pre-stained body of [8] to [9] below 0 015 under the conditions of a measurement frequency of 1 GHz and a temperature of 23 ° C. [1 1] The ratio of the epoxy group of the aromatic epoxy resin of the component (A) and the component (B) of the aromatic cyanate compound in the epoxy resin composition is 1: 05 to 1: 3 For a total of 100 parts by weight of the component (A) and the component (B), the phenoxy resin of the component (C) is blended with 3 ~ 4 0 S amount (5) (5) 200400242 parts of this [8] ~ [10] The pre-stained body. [12] A multilayer printed circuit board with an insulating layer formed by the pre-stained bodies of [8] to [Π]. [1 3] The [8] ~ [1 [] pre-stained body is laminated with plastic under pressure and heating conditions on the circuit board and hardened to form an insulation layer. If necessary, the surface of the insulation layer is roughened with an oxidizing agent. A method for manufacturing a multilayer printed circuit board characterized by forming steps included in the plated conductor layer. [1 4] A multilayer printed circuit board obtained by the manufacturing method of [1 3]. [Embodiments of the Invention] Hereinafter, the present invention will be described in detail. The component (A) of the present invention, "the aromatic aromatic epoxy resin having 2 or more epoxy groups in one molecule" refers to one having 2 or more epoxy groups in one molecule, and 'the molecule having an aromatic ring skeleton in the molecule. Epoxy resin. As an ideal example of an aromatic epoxy resin having 2 or more epoxy groups in one molecule, such as: bisphenol A type epoxy resin, bisphenol ρ type epoxy resin, bisphenol s type epoxy tree, Phenolic epoxy resin for phenol paint, phenolic epoxy resin for alkyl phenol paint, biphenyl epoxy resin, dicyclopentadiene epoxy resin, aromatic aldehyde with benzoic acid and phenolic hydroxyl group Examples of mutual condensate epoxide, naphthalene-type epoxy resin, triglycidyl-trimeric isocyanate, and the like include brominated fluorinated epoxy resins and phosphorus-modified epoxy resins. These epoxy resins may be used alone or in combination of two or more kinds. In the component (B) of the present invention, “having 2 or more cyanooxy groups in one molecule < an aromatic cyanate compound in one molecule” means having 2 or more oxygen (6) (6) 200400242 groups in one molecule, and, A cyanate compound having an aromatic ring skeleton in the molecule is an ideal example of an aromatic cyanate compound having 2 or more cyanooxy groups in a molecule such as: bisphenol A dicyanate, polyphenol cyanide Acid esters (oligo (3-methylene-1,5-diphenylcyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), 4,4 Examples of '-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, these prepolymers partially triazinated, etc. These cyanate compounds can be used separately, or It can be used in combination of two or more types. The ratio of epoxy groups present in one molecule of component (A) and cyano groups present in one molecule of component (B) in the epoxy resin composition is 1: 0 5 to 1. : 3 is preferred. If it is not within this range, a sufficiently low induced tangent cannot be obtained by the remaining unreacted epoxy or cyano groups after curing. In addition, the epoxy resin composition has a component (A) To When the epoxy compound is a cyano compound other than the component (B), these components also include those in which the ratio of the epoxy group to the cyano group is within this range. That is, the epoxy resin present in the epoxy resin composition The ratio of the cyano group to the cyanooxy group is preferably: 0 5 to 1 ·· 3. Hereinafter, the "phenoxy resin having a weight average molecular weight of 5000 to 100,000" of the component (C) of the present invention is performed. Explanation: The phenoxy resin is a polymer formed from the reaction product of a bifunctional epoxy resin and a bisphenol compound, and the hydroxyl group present in the molecule shows the hardening effect of the epoxy group and the cyano group. It is thought that the hardening properties (heat resistance, low electrical tangent, etc.) can be effectively exhibited at a lower hardening temperature. In a resin composition formed by a cyanate compound and an epoxy resin, the epoxy resin has hydroxyl groups to promote hardening. However, the useful life of the resin composition which is deteriorated by this hydroxyl group is known. In addition, the present inventors used polymer phenoxy resin in ingredients (A) and 3 ((7) (7) 200400242 B). After the component (C), there is no deterioration of the epoxy resin composition. Applicable period, and those with good hardened physical properties appear. By adding the phenoxy resin as the component (C), the roughening property of the epoxy resin hardened oxidant can be improved, and the conductor layer can also be formed by electroplating. Examples of phenoxy resins having a weight average molecular weight of 5,000 to 100,000 are: Phenonot YP 50 (manufactured by Toto Kasei Co., Ltd.) of bisphenol A type, E- 1 2 5 6 (Japanese epoxy resin (stock )), And other examples of brominated phenoxy resin Phenotot YP B40 (manufactured by Tohto Kasei Co., Ltd.), etc. As the component (C), the weight average molecular weight of the biphenyl skeleton is 5 000 ~ A phenoxy resin of 100,000 is ideal for heat resistance, moisture resistance and hardening promotion. Specific examples of this phenoxy resin are phenoxy resins formed by the reaction of biphenyl epoxy resins (YX 40000, manufactured by Japan Epoxy Resins Co., Ltd.) with various bisphenol compounds, YL 6742BH30, Examples of YL6835BH40, YL6953BΗ30, YL6954BH30, YL6974BH30, ΥΧ8100ΒΗ30. These phenoxy resins may be used alone or in combination of two or more kinds. The phenoxy resin with a weight average molecular weight of 5000 to 100,000 can not only promote the hardening effect, but also easily improve the mobility of the adhesive film and the pre-stained body, and also improve the mechanical strength and activity of the hardened material. Sex. And, 'can be roughened by the hardened material oxidant. In addition, when the weight average molecular weight of the component (C) resin is less than 5,000, the effect will be insufficient. Otherwise, if the weight average molecular weight is more than 10,000, the solubility of the epoxy resin and the organic solvent will be -10- (8) (8) 200400242 is significantly reduced, which is actually not easy to use. The compounding amount of the component (C) varies depending on the type. Generally, when the total amount of the component (A) epoxy resin and the component (B) cyanate compound is 00 parts by weight, the compounding ratio is 3 to 40. Part by weight is preferred. It is particularly preferably 5 to 25 parts by weight. When it is less than 3 parts by weight, the hardening accelerating effect of the resin composition is insufficient. When the resin composition is laminated (laminated) on a circuit board, or when the resin composition of the thermosetting laminate is cured, the resin fluidity becomes Too large, uneven thickness of the insulation layer. In addition, roughening of the hardened material due to the formation of the conductive layer was not obtained. Conversely, if it exceeds 40 parts by weight, the functional group of the phenoxy resin is excessive, and a sufficiently low induced tangent cannot be obtained. Furthermore, the fluidity when the resin composition is laminated to the circuit board is too low, which makes it exist in the circuit. The perforation of the substrate and the resin filling in the ventilation holes cannot be performed effectively. The total content of these components (A) to (C) in the epoxy resin composition of the present invention is not particularly limited. Generally, when the epoxy resin composition is 100% by weight, the total content is 25% to 90%. Weight percent is appropriate. The epoxy resin composition of the present invention can also be used as an organometallic compound used as a curing catalyst for the purpose of shortening the curing time when necessary. In the previous system, after the organometallic compound was used, the gel time during heat curing was limited by the amount of hundreds of ppm of the trace amount of the organometallic compound added, which was difficult to control. However, the organometallic compound in the epoxy resin composition of the present invention has auxiliary curing. Function, so even when the organometallic catalyst is added, it is easy to control the gel time. It can provide industrial-adhesive films suitable for multilayer printed circuit boards and pre--11-(9) (9) 200400242 stainers . Examples of organometallic compounds include organic copper compounds such as copper (11) acetamidine acetone ligands, organic zinc compounds such as zinc (II) acetamidine ligands, and cobalt (II) acetamidine acetone ligands. Examples of organic cobalt compounds such as cobalt (III) acetoacetone ligand. The amount of the organometallic compound added is generally based on the component (B), "i-Cyanooxy aromatic cyanate compound having 2 or more in i molecule", and is preferably 10 to 500 ppm after conversion to metal, and more preferably 25 to 200 ppm. In the epoxy resin composition of the present invention, if necessary, in order to reduce the thermal expansion of the formed insulating layer, an inorganic concrete filling material may be added. The addition amount of the inorganic rhenium filling material depends on the characteristics of the epoxy resin composition of the present invention and the required function. Generally, when the epoxy resin composition is 100% by weight, it is preferably 10 to 75% by weight. It is 20 to 65% by weight. As inorganic filling materials such as: silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Examples of barium titanate, hafnium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Particularly preferred is silicon dioxide. The average particle size of the inorganic filler is preferably 5 μm or less. When the average particle diameter exceeds 5 μm, it becomes difficult to form a fine pattern when the circuit pattern is formed on the conductor layer. In addition, in order to improve the moisture resistance, the inorganic filler material is preferably surface-treated with a surface-treating agent such as a silane coupling agent. In addition to the ingredients in the epoxy resin composition of the present invention, other thermosetting resins, thermoplastic resins, and additives may be used when necessary, without impeding the effects of the present invention. Those who are thermosetting resins, such as ··························································· etc. Examples of acid anhydrous compounds, epoxy isocyanate resins, xylene resins, radical generators and polymerizable resins are used as hardeners for epoxy resins. Examples of thermoplastic resins are: polyimide resin, polyamidoimine resin, polyetherimine resin, polyshos resin, polyethersho resin, polydiphenyl ether resin, polycarbonate resin, polyetheretherketone Examples of resin and polyester resin. Examples of additives include organic fillers such as polysiloxane powder, nylon powder, fluorine powder, tackifiers such as organic modified dendritic clay, polychloroether resin, polysiloxane, fluorine-based, high Molecular defoamers or correctors, imidazole, thiazole, triazole, silane coupling agents and other adhesives, phthalocyanine, green, iodine, green, diazo yellow, carbon black, etc. Agent cases. The epoxy resin composition of the present invention can form a hardened body having good heat resistance and electrical characteristics. For example, it can form a hardened product that satisfies the induced tangent conditions of printed circuit boards used in high frequency fields (such as: 0 0 1 5 under the conditions of measuring the frequency of 1 GHZ and the temperature of 2 3 ° C). Hereinafter, the adhesive film of the present invention will be described. The epoxy resin composition (A) ~ (C) as an essential component is dissolved in an organic solvent to make a resin varnish, and then the base film (support film) of the support is applied, and then sprayed with hot air, etc. By drying the solvent, the adhesive film of the present invention can be produced. Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc. Examples include acetates, cellosolves, carbitols such as butyl carbitol, aromatic hydrocarbon groups such as toluene and xylene, dimethylformamide, and dimethylacetamide N-methylpyrrolidone. Organic solvents can also be used in combination of -13- (11) (11) 200400242 or more. The practitioner can set appropriate and ideal drying conditions through simple experiments. For example, lacquers containing 30 to 60% by weight of organic solvents can be dried at 80 to 100 ° C for 3 to 10 minutes. The amount of organic solvent remaining in the epoxy resin composition is generally 10% by weight. The following is preferable, and the content is preferably 5% by weight or less. The adhesive film of the present invention preferably has an appropriate melt viscosity property when the epoxy resin composition layer constituting the adhesive film is used in a vacuum lamination plastic method. That is, after the film for adhesion of the present invention is softened under the temperature conditions of the vacuum laminated plastic (generally 70 ° C ~ 14 ° C), when the fluidity, perforations, and vent holes exist, the plastic is vacuum laminated. It is advisable to fill the hole with resin at the same time. This melting viscosity characteristic is disclosed in WO 01/97 5 82 and can be determined based on the temperature-melting viscosity curve obtained by measuring the dynamic viscoelasticity of the epoxy resin composition. The measurement start temperature was 60 ° C. After heating at 5 ° C / min to measure the melting viscosity, after calculating the temperature-melting viscosity curve, the first table represents the melting viscosity at each temperature. Ideal film for adhesion. -14- (12) 200400242

溫度（°c ) 熔解黏度（P 0 i S e ) 90 4,000〜5 0,000 100 2,000-2 1,000 110 900〜1 2,000 120 5 0 0 〜9,000 130 300〜15,000Temperature (° c) Melt viscosity (P 0 i S e) 90 4,000 ~ 5 0,000 100 2,000-2 1,000 110 900 ~ 1 2,000 120 5 0 0 ~ 9,000 130 300 ~ 15,000

該業者依本發明環氧樹脂組成物與黏接用薄膜相關之 揭示及WO 0 1 /97 5 82號公報之揭示，可易於調製適於真空 層壓塑料法之具有熔解黏度特性的理想黏接用薄膜。 本發明黏接用薄膜中，於10〜200 μηι厚之支撐薄膜使 環氧樹脂組成物層之厚度進行層壓塑料之電路基板導體厚 度以上者宜，較佳者於10〜150 μηι之範圍下進行層形成。 環氧樹脂組成物層之支撐薄膜未密合面上更可層形成 以支擋薄膜爲基準之保護薄膜。保護薄膜之厚度以 ^40 μπι者宜。以保護薄膜進行保護後，可防止對於環氧樹脂 組成物層表面附著塵染等、損傷者。黏接用薄膜亦可呈滾 筒狀卷取貯存之。 做爲支撐體例者如：聚乙烯、聚氯化乙烯等聚烯烴、 聚乙烯對苯二甲酸酯（以下稱「PET」）、聚乙烯萘二甲 酸酯等聚酯、聚碳酸酯、聚亞胺，更如：脫模紙、銅箔、 鋁箔等金屬箔例者。支撐薄膜中除沈渣處理、電f:處理之 -15- (13) (13)200400242 外，亦可進行脫模處理。 又’做爲淸漆調製所使用之有機溶劑例者如：丙酮、 丁酮、環己酮等酮類、醋酸乙酯、醋酸丁酯、溶纖劑乙酸 酯、丙二醇單曱醚乙酸酯、卡必醇乙酸酯等醋酸酯類、溶纖 劑、丁基溶纖劑等溶纖劑類、卡必醇、丁基卡必醇等卡必醇 類、甲苯、二甲苯、等芳香族烴基、二甲基甲醯胺 '二甲 基乙醯胺等例。此等有機溶劑可分別單獨使用，亦可合倂 2種以上使用之。 做爲電路基板所使用之基板例者可使用玻璃環氧基 板、金屬基板、聚酯基板、聚亞胺基板、B T樹脂基板、熱 硬化型聚苯醚基板等。又，本發明中電路基板係指形成圖 案加工之導體層（電路）於如上述基板之單面或雙面者謂 之。另外，於導體層與絕緣層相互層形成後所成之多層印 刷電路板中，該多層印刷電路板之最外層單面或雙面呈圖 案加工導體層（電路）者亦含於本發明所謂之電路基板者 。又，導體層表面藉由黑化處理等之後，亦可預先進行粗 化處理。 以下針對本發明預漬體進行說明。 於纖維所成之薄片狀補強基材藉由熱融法或溶媒法浸漬 本發明環氧樹脂組成物，加熱呈半硬化後可製造預漬體。 亦即，環氧樹脂組成物可做成浸漬於纖維所成薄片狀補強 基材狀態之預漬體者。 做爲纖維所成薄片狀補強基材例者可使用如塗玻璃粉 砂布、芳香族聚醯胺合成纖維等，做爲預漬體用纖：、”二常 -16- (14) (14)200400242 用者。 熱熔融法係於有機溶劑中不溶解樹脂，暫時將樹脂塗 佈於樹脂與剝離性良好之塗工紙後，將此層壓塑料於薄片 狀補強基材，或藉由模塑塗層直接進行塗工等，製造預漬 體之方法。又，溶媒法係與黏接用薄膜相同，浸漬樹脂淸 漆於薄片狀補強基材後，進行乾燥之方法者，此時之乾燥 條件與黏接用薄膜相同者。 以下針對使用本發明黏接用薄膜，製造本發明多層印 刷電路板之方法，進行說明之。 本發明黏接用薄膜可藉由真空層合機後，適時於電路 基板進行層壓塑料之。層壓塑料中其黏接用薄膜具保護薄 膜時去除該保護薄膜後，使該黏接用薄膜進行加壓及加熱 之同時於電路基板上進行壓延之。層壓塑料之條件於必要 時使黏接用薄膜及電路基板進行預熱後，壓延瑕度爲 70〜140它、壓延壓力爲1〜111^€/(：1112，於空氣壓20111〇111§ 以下之減壓下進行層壓塑料者宜。又，層壓塑料之方法可 爲分批式，亦可以滾輥之連續式進行之。層壓塑料後，冷 卻至室溫附近後，必要時剝離支撐薄膜後，於電路基板進 行被層壓塑料之環氧樹脂組成物加熱硬化之，加熱硬化之 條件爲150 °C〜220 °C、20分鐘〜180分鐘之範圍者、更 理想之條件爲160 r〜200 t：、30分鐘〜12〇分鐘者。使 用施予脫模處理之支撐薄膜時，亦可於加熱硬化後進行支 撐薄膜之剝離。另外，使用金屬箔時其支撐薄膜亦可直接 做爲導體層使用，因此無需進行剝離之。 -17- (15) (15)200400242 做爲此環氧樹脂組成物硬化物者形成絕緣層後，必要 時於該絕緣層亦可藉由鈷頭、激光等進行開孔形成穿孔、 通氣孔。 再，藉由乾式電鍍、或濕式電鍍後形成導體層。做爲 乾式電鍍者可使用公知之蒸鍍、濺射、離子摩擦等方法者 ，濕式法時，首先以過錳酸鹽（過錳酸鉀、過錳酸鈉等） 、重鉻酸鹽、臭氧、過氧化氫/硫酸、硝酸等氧化劑進行硬 化環氧樹脂組成物層（絕緣層）表面之粗化處理後，形成 凹凸之簧片。氧化劑例特別以過錳酸鉀、過錳酸鈉等之氫 氧化鈉水溶液（鹼性過錳酸水溶液）爲理想使用者。再以 無電解電鍍與電解電鍍之組合方法形成導體層。又，導體 層於形成反圖案之電鍍光阻後，以無電解電鍍亦可形成導 體層者。之後形成圖案之方法具體例如：該業者公知的去 除法、半加成法等可使用之。 以下針對使用本發明預漬體後，製造本發明多層印刷 電路板之方法進行說明之。 做爲層壓塑料本發明預漬體於電路基板之方法例如： 將1片預漬體或必要時重疊數片，於其上介著脫模薄膜配 置金屬板後於加壓及加熱條件下藉由層合加壓機進行層壓 塑料之方法例者。此時，同時進行電路基板之預漬體層壓 塑料與硬化，壓力爲5〜4 Okgf /cm2，溫度爲120〜220 °C 、30〜180分鐘之範圍下進行層合，硬化者宜。又，與前述 黏接用薄膜相同藉由真空層合機，針對電路基板進行預漬 體之層壓塑料，之後亦可進行加熱硬化之。 -18- (16) (16)200400242 如此於電路基板形成做爲預漬體硬化物之絕緣層後， 與前述相同，必要時於絕緣層形成穿孔、通氣孔，使絕緣 層表面進行粗化之後，藉由電鍍形成導體層後可製造多層 印刷電路板。另外，觸模薄膜與預漬體間挾住銅箱等進行 層壓塑料後，金屬箔亦可直接做爲導體層使用之。 【實施方式】 [實施例] 以下藉由實施例進行本發明具體的說明，惟，本發明 未受限於此。 <實施例1 > 3 〇重量份做爲成份（A )之雙酚A型環氧樹脂（環氧 基虽量175’日本環氧樹脂（股份）製epik〇te 825) 、60 重里份做爲（B)成份之雙酣a二氯酸酯之預聚體（ Ronza Japan (股份）BA23 0S75、氰酸醋當量約232、不 揮發粉75%之丁酮（MEK)淸漆）、40重量份做爲成份 (C )含聯苯骨架之苯氧基樹脂淸漆（日本環氧樹脂（股 份）製YL6954BHjO、重量平均分子量38〇〇〇、不揮發份 3〇%之MEK /環己酮淸漆），更添加30重量份球型二氧化 矽後，製成環氧樹脂組成物。將該淸漆狀環氧樹脂組成物 以乾燥後厚度呈60 μηι之模塑塗層進行塗佈於厚度38 之PET薄膜後，於“〜丨⑼c下進行乾燥ι〇分鐘後，取 得黏接用薄膜（殘留溶媒約1〜2重量％ 。 -19- (17) (17)200400242 <實施例2>According to the disclosure of the epoxy resin composition and the adhesive film according to the present invention and the disclosure of WO 0 1/97 5 82, it is possible to easily prepare an ideal adhesive having melting viscosity characteristics suitable for the vacuum lamination plastic method. With film. In the adhesive film of the present invention, a support film having a thickness of 10 to 200 μηι is used to laminate the thickness of the epoxy resin composition layer to the thickness of the circuit board conductor of the plastic, and more preferably in the range of 10 to 150 μηι. Layer formation is performed. The non-adhered surface of the supporting film of the epoxy resin composition layer can be further formed into a protective film based on the supporting film. The thickness of the protective film is preferably ^ 40 μm. Protected with a protective film can prevent damage to the surface of the epoxy resin composition layer from dust and the like. The adhesive film can also be rolled and stored in a roll shape. Examples of supports include polyolefins such as polyethylene and polyvinyl chloride, polyethylene terephthalate (hereinafter referred to as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, and polyethylene. Imine, for example: metal foil such as release paper, copper foil, aluminum foil. In addition to sedimentation treatment and electrical f: treatment in the supporting film, (15) (13) (13) 200400242, it can also be demolded. Examples of organic solvents used in the preparation of lacquers include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl ether acetate. , Acetates such as carbitol acetate, cellosolves such as cellosolve, butyl cellosolve, carbitols such as carbitol, butylcarbitol, aromatic hydrocarbon groups such as toluene, xylene, Examples of dimethylformamide 'dimethylacetamide. These organic solvents may be used singly or in combination of two or more kinds. Examples of the substrate used for the circuit substrate include glass epoxy plates, metal substrates, polyester substrates, polyimide substrates, B T resin substrates, and thermosetting polyphenylene ether substrates. In the present invention, a circuit substrate refers to a conductor layer (circuit) that is patterned on one or both sides of the substrate. In addition, in a multilayer printed circuit board formed by forming a conductor layer and an insulating layer on each other, the outermost layer of the multilayer printed circuit board is patterned on one or both sides to process the conductor layer (circuit). Circuit board. After the surface of the conductive layer is subjected to a blackening treatment or the like, a roughening treatment may be performed in advance. The prepreg of the present invention will be described below. The sheet-like reinforcing substrate made of fibers is impregnated with the epoxy resin composition of the present invention by a hot-melt method or a solvent method, and a pre-stained body can be manufactured after being semi-hardened by heating. That is, the epoxy resin composition can be made into a pre-stained body impregnated in the state of a sheet-like reinforcing base made of fibers. As an example of the sheet-like reinforcing substrate made of fibers, glass frosted cloth, aromatic polyamide synthetic fibers, etc. can be used as the fiber for the pre-staining body :, "二 常 -16- (14) (14) 200400242 User: The hot-melt method does not dissolve the resin in organic solvents. After temporarily coating the resin on the resin and coated paper with good peelability, this laminated plastic is used to reinforce the substrate in a sheet shape, or by molding The method of manufacturing the pre-stained body by directly coating the coating, etc. The solvent method is the same as that of the film for adhesion, and the method of drying after impregnating the resin with lacquer on the sheet-like reinforcing substrate, and the drying conditions at this time The same as the film for adhesion. The method for manufacturing the multilayer printed circuit board of the present invention using the film for adhesion of the present invention is described below. The film for adhesion of the present invention can be applied to the circuit after the vacuum laminator in a timely manner. The substrate is laminated with plastic. When the adhesive film in the laminated plastic has a protective film, the protective film is removed, and then the adhesive film is pressed and heated while being rolled on the circuit substrate. The laminated plastic Condition After pre-heating the bonding film and the circuit board as necessary, the rolling defect is 70 to 140, and the rolling pressure is 1 to 111 ^ € / (: 1112, under a reduced pressure of air pressure 20111〇111§ Laminated plastics are preferred. In addition, the method of laminating plastics can be batch or continuous rollers. After laminating plastics, cool to room temperature, peel the support film if necessary, and then apply the circuit The substrate is heated and hardened by the epoxy resin composition of the laminated plastic. The conditions for the heat hardening are 150 ° C to 220 ° C, and the range is 20 minutes to 180 minutes. The more ideal condition is 160 r to 200 t: 30 minutes to 120 minutes. When using a support film that has been subjected to a mold release treatment, the support film can also be peeled off after heating and curing. In addition, when a metal foil is used, the support film can also be used directly as a conductor layer, so No peeling is required. -17- (15) (15) 200400242 After forming an insulating layer for the hardened epoxy resin composition, if necessary, the insulating layer can be formed with a cobalt head, laser, etc. Perforated, vented. The conductive layer is formed after electroplating or wet electroplating. As a dry electroplater, a known method such as evaporation, sputtering, ion friction, etc. can be used. In the wet method, firstly, permanganate (potassium permanganate, potassium permanganate, After roughening the surface of the hardened epoxy resin composition layer (insulating layer), such as oxidants such as sodium permanganate, dichromate, ozone, hydrogen peroxide / sulfuric acid, and nitric acid, roughened springs are formed. Examples of oxidants In particular, an aqueous solution of sodium hydroxide (aqueous solution of alkaline permanganate) such as potassium permanganate, sodium permanganate, etc. is an ideal user. The conductor layer is formed by a combination of electroless plating and electrolytic plating. Furthermore, the conductor layer is After forming a counter-patterned photoresist, a conductor layer can also be formed by electroless plating. Specific methods for forming a pattern afterwards include, for example, removal methods and semi-additive methods known to the practitioner. The method for manufacturing the multilayer printed circuit board of the present invention after using the pre-stained body of the present invention will be described below. As a method for laminating the plastic pre-stained body of the present invention on a circuit substrate, for example: 1 piece of pre-stained body or several sheets may be overlapped if necessary, and a metal plate is arranged through a release film thereon under pressure and heating conditions. An example of a method for laminating plastic by a laminating press. At this time, the pre-stained body laminated plastic and hardening of the circuit board are simultaneously performed, and the lamination is performed at a pressure of 5 to 4 Okgf / cm2, a temperature of 120 to 220 ° C, and a range of 30 to 180 minutes. Hardening is preferred. In addition, similar to the above-mentioned adhesive film, a vacuum laminator is used to pre-stain a laminated plastic on a circuit board, and then it may be heat-hardened. -18- (16) (16) 200400242 After forming the insulating layer of the circuit board as the hardened body of the pre-stained body in this way, the same as before, if necessary, through holes and vent holes are formed in the insulating layer to roughen the surface of the insulating layer. After forming the conductor layer by electroplating, a multilayer printed circuit board can be manufactured. In addition, the metal foil can also be used directly as a conductive layer after laminating plastic by holding a copper box between the touch film and the pre-stained body. [Embodiments] [Examples] The present invention will be specifically described below by way of examples, but the present invention is not limited thereto. < Example 1 > 30 parts by weight as a component (A) of a bisphenol A type epoxy resin (with an epoxy group amount of 175 'Epik〇te 825 manufactured by Japan Epoxy Resin Co., Ltd.), 60 parts by weight Prepolymer of bis (a) dichlorochloride (B) (Ronza Japan (shares) BA23 0S75, cyanate equivalent about 232, non-volatile powder 75% methyl ethyl ketone (MEK) lacquer), 40 As a component (C), a phenoxy resin lacquer containing a biphenyl skeleton (YL6954BHjO manufactured by Japan Epoxy Resin (Shares) Co., Ltd., MEK / cyclohexanone with a weight average molecular weight of 38,000 and a nonvolatile content of 30% Lacquer), and 30 parts by weight of spherical silica was added to prepare an epoxy resin composition. This lacquer-like epoxy resin composition was coated on a PET film having a thickness of 60 μm with a mold coating having a thickness of 60 μm after drying, and then dried at “~ 丨 c” for 0 minutes to obtain adhesion. Film (about 1 to 2% by weight of residual solvent. -19- (17) (17) 200400242 < Example 2 >

，變更實施例1之成份（C )苯氧基樹脂爲3 0重量份之 雙酚 A型苯氧基樹脂、淸漆（曰本環氧樹脂（股份）製 E1256B40、重量平均分子量48000、不揮發份40%之MEK 淸漆）之外，同法將環氧樹脂組成物以乾燥後厚度呈60 μπι之模塑塗層進行塗佈於厚度38 之PET薄膜後’於 8 0〜12 0 t：下，進行乾燥10分鐘’取得黏接用薄膜（殘留 溶媒約1〜2重量％ ) ° <實施例3 > 於塗玻璃粉之紗布浸漬實施例1之環氧樹脂組成物淸 漆後，於1 5 0 °C下進行乾燥8分鐘後，取得厚度〇 1 mm 之預漬體（預漬體中含環氧樹脂組成物量4 5重量％，殘 留溶媒約1〜2重量％ )。 <比較例1 > 除未含成份（c )之苯氧基樹脂之外，與實施例1之 環氧樹脂組成物同法將環氧樹脂組成物以乾燥後厚度呈 60 μηι之模塑塗層進行塗佈於厚度38 μηι之PET薄膜後， 8 0〜120 °C下進行乾燥1〇分鐘，惟，乾燥中低粘度過低而 出現部份樹脂彈出（穿孔），乾燥後樹脂表面仍具粘著性 ，無法製造出做爲黏接用薄膜可耐用者。 -20- (18) (18)200400242 <比較例2 > 變更成份（C )之苯氧基樹脂爲6 0重量份之聚砸（Change the component (C) phenoxy resin in Example 1 to 30 parts by weight of bisphenol A-type phenoxy resin, lacquer (E1256B40 made by Ben Epoxy Resin (stock), weight average molecular weight 48000, non-volatile In addition to 40% of MEK lacquer), the epoxy resin composition was coated on a PET film having a thickness of 60 μm with a mold coating having a thickness of 60 μm after drying. Next, it was dried for 10 minutes to obtain a film for adhesion (about 1 to 2% by weight of residual solvent) ° < Example 3 > The glass epoxy-coated gauze was impregnated with the epoxy resin composition varnish of Example 1, After drying at 150 ° C for 8 minutes, a pre-stained body having a thickness of 0.01 mm was obtained (the pre-stained body contained 45.5% by weight of the epoxy resin composition, and the residual solvent was about 1 to 2% by weight). < Comparative Example 1 > Except for the phenoxy resin containing no component (c), the epoxy resin composition was molded in the same manner as the epoxy resin composition of Example 1 to a thickness of 60 μm after drying. After the coating is applied to a PET film with a thickness of 38 μm, it is dried at 80 ~ 120 ° C for 10 minutes. However, the resin has a low viscosity during drying and some resin pops up (perforation). The resin surface is still dry after drying. It is tacky and cannot be made durable as an adhesive film. -20- (18) (18) 200400242 < Comparative Example 2 > Change the phenoxy resin of component (C) to 60 parts by weight of poly (

Solvay advanced polymers (股份）製 P-1700)之不揮發 分2 0%N ’ N•-二甲基甲醯胺淸漆之外，與實施例1同法將 環氧樹脂組成物以乾燥後厚度呈60 μπα之模塑塗層進行塗 佈於厚度3 8 μ m Ρ Ε Τ薄膜後，於8 0〜1 2 0 °C下乾燥1 〇分 鐘’取得黏接用薄膜（殘留溶媒約i〜2重量。/。）。 鲁 <比較例3 > 變更成份（C)之苯氧基樹脂爲1〇重量份之苯酚漆用 酚醛樹脂（大日本油墨化學工業（股份〇製T D 2 0 9 0 - 6 0 Μ， 不揮發份60%之ΜΕΚ淸漆）之外，與實施例1同法將環 氧樹脂組成物以乾燥後厚度爲6 0 μηι之模塑塗層進行塗佈 於厚度38 μπι PET薄膜後，於80〜120 °C下乾燥10分鐘 ，取得黏接用薄膜（殘留溶媒1〜2重量％ )。 <實施例4> 由35 μπι銅箔，0 2mm板厚之FR4雙面貼銅層合板製 作電路基板後’使實施例1取得之黏接用薄膜藉由間歇式 真空層壓機，於溫度1 1〇 t ，壓力5kgf /cm2、氣壓 5m mHg以下’ 30秒力p壓之條件下於兩面進行層壓塑料後 ，剝離PE T薄膜，於1 7 0 °C下加熱硬化3 0分鐘。之後， 藉由激光進行開孔，形成穿孔，再以過錳酸鹽之鹼性氧化 劑進行硬化後環氧樹脂組成物表面之粗化處理後，進行無 -21 - (19) (19)200400242 電解及電解電鍍後依去除法形成圖案，取得4層印刷電路 板。隨後，更於1 8 0 °C進行鍛燒處理9 0分鐘。取得導體 層之起毛強度爲〇 7kgf /cm者。又’起毛強度測定依日本 工業規格（JI S ) C 6 4 8 1爲基準進行評定後’導體電鍍厚 度爲3 0 μ m。將取得多層印刷電路板於2 6 0 °C下進行焊 錫浸漬6 0秒，觀察焊錫耐熱性結果無樹脂之層離、導體 之剝離等異常現象。 <實施例5 > 使用實施例2取得之黏接用薄膜’與實施例4同法取 得4層印刷電路板，所取得導體層之起毛強度爲〇 8 kgf /cm者。取得多層印刷電路板於260 °C下進行焊錫浸漬 6 〇秒，觀察焊錫耐熱性後，結果無樹脂之層離，導體剝 離等異常現象。 <實施例6 > 重疊2片實施例3取得之預漬體，介著脫模薄膜^金 屬板挾住，於120 °C，lOkgf /cm2下進行層合加壓15分 鐘後，更於170 °C，40kgf /cm2進行層合加壓60分鐘後’ 取得0.2mm板厚之層合板。再以過錳酸鹽之鹼性氧化劑進 行表面之粗化處理後，整體藉由無電解及電解電鍍形成導 體層。之後，更於180 °C下進行鍛燒處理60分鐘。所取得 之導體層起毛強度爲0.7kg f /cm者。取得多層印刷電路板 於260 °C，進行焊錫浸漬60秒，進行觀察焊錫耐熱性結 (20) (20)200400242 果無樹脂之層離’導體剝離等異常現象。 <比較例4〉 利用比較例2取得之黏接用薄膜與實施例4同法取得 4層印刷電路板。所取得導體層之起毛強度爲〇 2 k g f / c m 。將取得多層印刷電路板於2 6 0 °C下進行焊錫浸漬6 0秒 後，觀察焊錫耐熱性之結果出現起毛強度太低，導致導體 剝離之異常現象。 <樹脂組成物之硬化作動測定> 利用（股份）UBM公司製型式 Rheosol-G3000，進 行實施例1、2及比較例2取得黏接用薄膜之環氧樹脂組 成物動粘彈性之測定，實施例1、2及比較例2之測定結 果如圖1所示。測定方式係由初期溫度60 °C以昇溫速度 5 °C /分鐘，測定間隔溫度2 5 °C，振動數1Hz /deg進行 之。由圖1顯示，實施例1、2中出現由13 0 t伴隨硬化 之熔解黏度上昇以1 7 0度以上之急劇上昇者，而未含苯氧 基樹脂之比較例2中，至2 0 0 °C附近未再出現粘度上昇 。由此證明，實施例1、2之樹脂組成物於低溫下仍可硬 化。以下各溫度中熔解黏度値示於第2表〜第4表。 -23- (21)200400242 第2表 實施例1樹脂組成物之溫度-熔解黏度値 溫度（°c ) 熔解黏度（poise ) 90 約 9 020 1 00 約 4 6 5 0 110 約 2 8 8 0 1 20 約 2 0 5 0 13 0 約 1 7 8 0Solvay advanced polymers (P-1700, manufactured by Co., Ltd.) with a non-volatile content of 20% N'N • -dimethylformamide varnish, the thickness of the epoxy resin composition was dried in the same manner as in Example 1 After applying a 60 μπα molded coating to a 3 8 μm ΡΕΤ film, it was dried at 80 to 120 ° C for 10 minutes to obtain a film for adhesion (residual solvent about i ~ 2 weight./.). Lu < Comparative Example 3 > Changing the phenoxy resin of the component (C) to 10 parts by weight of a phenolic resin for phenol paint (Dai Nihon Ink Chemical Industry Co., Ltd. TD 2 0 9 0-6 0 M, no Except for 60% volatile matter (MEKY paint), the epoxy resin composition was dried in a thickness of 60 μηι with a mold coating having a thickness of 60 μηι and coated with a PET film having a thickness of 60 μηι. Dry at ~ 120 ° C for 10 minutes to obtain a film for adhesion (residual solvent 1 to 2% by weight). ≪ Example 4 > FR4 double-sided copper-clad laminate with 35 μm copper foil and 0 2 mm thickness was used to make a circuit After the substrate, the film for adhesion obtained in Example 1 was performed on both sides by an intermittent vacuum laminator at a temperature of 110 ft, a pressure of 5 kgf / cm2, and an air pressure of 5 m mHg or less. After laminating the plastic, peel the PET film and heat-harden it at 170 ° C for 30 minutes. After that, open the hole with a laser to form a perforation, and then harden it with an alkaline oxidant of permanganate. After roughening the surface of the resin composition, -21-(19) (19) 200400242 electrolytic and electrolytic After plating, a pattern was formed by the removal method to obtain 4 layers of printed circuit boards. Subsequently, it was subjected to a calcination treatment at 180 ° C for 90 minutes. Those with a raised hair strength of the conductive layer of 0,7 kgf / cm were obtained. After evaluation based on Japanese Industrial Standards (JI S) C 6 4 8 1 'the thickness of the conductor plating is 30 μm. The obtained multilayer printed circuit board is solder immersed at 60 ° C for 60 seconds, and the solder is observed As a result of heat resistance, there were no abnormalities such as resin delamination and conductor peeling. ≪ Example 5 > Using the adhesive film obtained in Example 2 ', a 4-layer printed circuit board was obtained in the same manner as in Example 4, and the conductor was obtained. A layer with a fluffing strength of 0.8 kgf / cm. Obtain a multilayer printed circuit board and perform solder dipping at 260 ° C for 60 seconds. After observing the solder heat resistance, there is no abnormality such as resin delamination and conductor peeling. ≪ Example 6 > Two pieces of the pre-stained body obtained in Example 3 were stacked, sandwiched through a release film ^ metal plate, laminated and pressed at 120 ° C, 10 kgf / cm2 for 15 minutes, and then more than 170 ° C, after laminating and pressing at 40kgf / cm2 for 60 minutes, 0.2mm was obtained Thick laminated board. After roughening the surface with alkaline oxidant of permanganate, the entire conductor layer is formed by electroless and electrolytic plating. After that, it is calcined at 180 ° C for 60 minutes. The obtained conductor layer has a fluffing strength of 0.7kg f / cm. Obtain a multilayer printed circuit board at 260 ° C, perform solder immersion for 60 seconds, and observe the solder heat resistance. (20) (20) 200400242 Delamination without resin 'Anomalies such as conductor stripping. < Comparative Example 4 > A four-layer printed circuit board was obtained in the same manner as in Example 4 using the adhesive film obtained in Comparative Example 2. The fuzzing strength of the obtained conductor layer was 0 2 k g f / c m. The obtained multilayer printed circuit board was subjected to solder immersion at 60 ° C for 60 seconds, and the solder heat resistance was observed. As a result, the fluffing strength was too low, leading to the abnormal phenomenon of conductor peeling. < Measurement of hardening action of resin composition > The measurement of the dynamic viscoelasticity of the epoxy resin composition obtained in Examples 1, 2 and Comparative Example 2 using the Rheosol-G3000 made by UBM Co., Ltd., The measurement results of Examples 1, 2 and Comparative Example 2 are shown in FIG. 1. The measurement method is performed from an initial temperature of 60 ° C at a temperature increase rate of 5 ° C / min, a measurement interval temperature of 25 ° C, and a vibration frequency of 1 Hz / deg. As shown in FIG. 1, in Examples 1 and 2, the melting viscosity increased by 13 0 t accompanied by hardening increased sharply to 170 degrees or more, and in Comparative Example 2 without phenoxy resin, it reached 2 0 0. No increase in viscosity occurred near ° C. This proves that the resin compositions of Examples 1 and 2 can be hardened at a low temperature. The melting viscosities at the following temperatures are shown in Tables 2 to 4. -23- (21) 200400242 Table 2 Example 1 Temperature of the resin composition-melting viscosity 値 temperature (° c) melting viscosity (poise) 90 about 9 020 1 00 about 4 6 5 0 110 about 2 8 8 0 1 20 Approx. 2 0 5 0 13 0 Approx. 1 7 8 0

第3表 實施例2樹脂組成物之溫度-熔解黏度値 溫度（°C ) 熔解黏度（poise ) 90 約 7 4 1 0 1 00 約 3 2 1 0 110 約 1 8 1 0 1 20 約 1290 13 0 約 1 0 7 0Table 3 Example 2 Temperature of the resin composition-melting viscosity 値 temperature (° C) melting viscosity (poise) 90 about 7 4 1 0 1 00 about 3 2 1 0 110 about 1 8 1 0 1 20 about 1290 13 0 Approx. 1 0 7 0

-24- (22)200400242 第4表 比較例2 樹脂組成物之溫•熔解黏度値 溫度（t:) 熔解黏度（P 〇 i S e ) 90 約 18100 1 00 約 10300 110 約 6670 120 約 4 8 5 0 13 0 約 3 9 5 0-24- (22) 200400242 Table 4 Comparative Example 2 Temperature and Melting Viscosity 値 Temperature of Resin Composition (t :) Melting Viscosity (P 〇i S e) 90 about 18100 1 00 about 10300 110 about 6670 120 about 4 8 5 0 13 0 approx. 3 9 5 0

<樹脂組成物之適用期評定> 與上述相同測定比較例3取得之黏接用薄膜環氧樹脂 組成物之動粘彈性。又，室溫下保存實施例1、2及比較例 2、3取得黏接用薄膜之環氧樹脂組成物3天後，與上述同 法進行測定動粘彈性。圖2顯示比較例3保存前後之結果 。針對實施例1、2及比較例2之樹脂組成物證明，繪出與 保存前幾乎相同之曲線（圖中省略），呈良好之適用期。 另外’以苯酚樹脂做爲硬化促進劑使用之比較例3被證明 ’室溫下，保存3天後，其樹脂熔融粘度極端上昇，適用 期不良，無法有效做爲黏接用薄膜、預漬體用之樹脂組成 物之使用。合倂圖1之結果證明，實施例1、2取得之黏 胃ffl薄膜環氧樹脂組成物藉由苯氧基樹脂後可兼具促進硬 化效果及良好適用期。 <電氣特性之評定 -25- (23) (23)200400242 實施例1、2及比較例2取得黏接用薄膜之環氧樹脂 組成物相互重疊進行真空層壓塑料法後，剝離支撐薄膜後 ，複數次重覆進行同樣的樹脂組成物面相之真空層壓塑料 法後，製作1 6層60 μπι樹脂，約1 mm厚度之樹脂組成物 樣品。將此於1〇〇 °C、30分鐘，更於18〇 °C、9〇分鐘 進行熱硬化。使用本樣品，依IPC-TM6 5 0、2 5 5 9爲基 準進行測定誘電率、誘電正切。第5表記載室溫（2 3 °C )，測定周波數1 GHz之測定値結果。 第5表 實施例1 實施例2 比較例2 誘電率 3 1 3 2 3.3 誘電正切 0 010 0 012 0 019 另外，由第5表結果證明，本發明樹脂組成物於1 8 0 °C之硬化條件下可發揮良好電氣特性（1 GHz，23 °C之誘 電正切0 01 5以下）。又，比較例2之樹脂本身誘電正切 中具有低於苯氧基樹脂之値的聚硕使用後仍顯示高誘電正 b刀値之樹脂組成物硬化物。 又，由實施例4〜6、比較例4證明，本發明黏接用薄 膜及預漬體可藉由氧化劑粗化後形成良好密合性之銅電鍍 ，可以積累方式簡便取得多層印刷電路板。 -26- (24) (24)200400242 [產業上可利用性] 本發明黏接用薄膜及預漬體具良好適用期及硬化特性 ’且，硬化後可發揮良好電氣特性。又，硬化後可藉由氧 化劑粗化硬化物，而可藉由電鍍形成導體層，特別是藉由 積累方式之製造可做爲工業用多層印刷電路板之良好黏接 用薄膜及預漬體。 【圖式簡單說明】 圖1係代表構成實施例1、2及比較例2所取得之黏著薄 膜h氧樹脂組成物之動態黏彈性所測定之結果者。 ® 2係於室溫下保存構成比較例3取得之黏接用薄膜環 氧樹脂組成物保存3天前後所測得動粘彈性之結果。 -27-< Evaluation of pot life of resin composition > The dynamic viscoelasticity of the thin film epoxy resin composition for adhesion obtained in Comparative Example 3 was measured in the same manner as described above. In addition, after the epoxy resin composition of the adhesive film was stored at room temperature for Examples 1 and 2 and Comparative Examples 2 and 3 for 3 days, the dynamic viscoelasticity was measured in the same manner as described above. Figure 2 shows the results of Comparative Example 3 before and after storage. For the resin compositions of Examples 1, 2 and Comparative Example 2, it was proved that the curve almost the same as that before storage (omitted in the figure) was drawn, showing a good pot life. In addition, 'Comparative Example 3 using a phenol resin as a hardening accelerator was proved' After storage at room temperature for 3 days, the resin melt viscosity increased extremely, and the pot life was not good, and it could not be effectively used as an adhesive film or pre-stained body. Use of resin composition. Combining the results of Fig. 1 proves that the gastric ffl thin film epoxy resin composition obtained in Examples 1 and 2 can have both a hardening effect and a good pot life by using a phenoxy resin. < Evaluation of electrical characteristics-25- (23) (23) 200400242 Example 1, 2 and Comparative Example 2 The epoxy resin compositions obtained from the adhesive film were overlapped with each other, and after the vacuum lamination plastic method, the support film was peeled off After repeatedly carrying out the vacuum lamination plastic method of the same resin composition surface repeatedly, 16 layers of 60 μm resin and a resin composition sample of about 1 mm thickness were produced. This was heat-cured at 100 ° C for 30 minutes, and further at 180 ° C for 90 minutes. Use this sample to determine the induction rate and induction tangent based on IPC-TM6 50, 2 5 59. Table 5 describes the measurement results of room temperature (2 3 ° C) and the measured cycle frequency of 1 GHz. Table 5 Example 1 Example 2 Comparative Example 2 Inductive Rate 3 1 3 2 3.3 Inductive Tangent 0 010 0 012 0 019 In addition, it is proved from the results in Table 5 that the resin composition of the present invention is hardened at 180 ° C Can exhibit good electrical characteristics (at 1 GHz, 23 ° C induced tangent below 0 01 5). In addition, the resin itself of Comparative Example 2 had a resin composition hardened product having a higher electromotive tangent b-knife than the phenoxy resin tangent which had a lower fluorene than the phenoxy resin. Furthermore, it is proved from Examples 4 to 6 and Comparative Example 4 that the adhesive film and the pre-stained body of the present invention can be roughened by an oxidizing agent to form a copper plating with good adhesion, and a multilayer printed circuit board can be easily obtained by an accumulation method. -26- (24) (24) 200400242 [Industrial Applicability] The adhesive film and prepreg according to the present invention have a good pot life and hardening characteristics ′, and can exhibit good electrical properties after hardening. In addition, after hardening, the hardened material can be roughened by an oxidizing agent, and the conductor layer can be formed by electroplating. Especially, it can be used as a good adhesion film and a pre-stained body for industrial multilayer printed circuit boards by the accumulation method. [Brief description of the drawings] FIG. 1 represents the results of measurement of the dynamic viscoelasticity of the adhesive thin film h-oxygen resin composition obtained in Examples 1, 2 and Comparative Example 2. ® 2 is stored at room temperature and constitutes the result of measurement of the viscoelasticity of the thin film epoxy resin composition obtained in Comparative Example 3 before and after storage for 3 days. -27-

Claims (1)

(1) (1)200400242 拾、申請專利範圍 1 一種黏接用薄膜，其特徵爲含有下記成份（& )〜（ c)之環氧樹脂組成物，於支撐薄膜上形成層者， (A ) 1分子中具2以上環氧基的芳香族系環氧樹脂 (B ) 1分子中具2以上氰氧基的芳香族系氰酸酯化 合物，及 籲 c C )重量平均分子量爲5000〜100，000之苯氧基樹脂 〇 2如申請專利範圍第〗項之黏接用薄膜，其中該成份 (C )之苯氧基樹脂爲具有聯苯基骨架之苯氧基樹脂者。 3如申請專利範圍第1項或第2項之黏接用薄膜，其中 該環氧樹脂組成物加熱硬化後之誘電正切於測定周波數 1 GHz及溫度23 °C之條件下爲〇 〇15以下者。 4如申請專利範圍第〗項或第3項之黏接用薄膜，其 0 中該環氧樹脂組成物中成份（A )之芳香族系環氧樹脂的 環氧基與成份（B )之芳香族系氰酸酯化合物的氰氧基相 互比例爲1 ·· 0 5〜1 ·· 3者，針對1 〇 〇重量份之成份（A)與 成份（B )總量配合成份（C )之苯氧基樹脂爲3〜40重量 份者。 5 —種多層印刷電路板，其特徵爲藉由如申請專利範 圍第1項至第4項黏接用薄膜形成絕緣層者。 6 —種多層印刷電路板之製造方法，其特徵爲含有藉 由如申請專利範圍第1項至第4項之黏接用薄膜以加壓及 -28- (2) (2)200400242 加熱條件下進行層壓塑料於電路基板後，必要時剝離支撐 薄膜後’使層壓塑料於電路基板之環氧樹脂組成物進行加 熱硬化後形成絕緣層之後，未剝離支撐薄膜時，於必要時 將之剝離後，必要時以氧化劑進行該絕緣層表面之粗化， 藉由電鍍形成導體層之步驟者。 7 —種多層印刷電路板，其特徵爲藉由如申請專利範 圍第6項之製造方法所取得者。 8 —種預漬體，其特徵係將含下記成份（a )〜（c ) 之環氧樹脂組成物浸漬於纖維所成薄片狀之補強基材者， (A) 1分子中具有2以上環氧基之芳香族系環氧樹 脂， (B) 1分子中具有2以上氰氧基之芳香族系氰酸酯 化合物，以及 (C) 重量平均分子量爲5000〜100，000之苯氧基樹脂 〇 9如申請專利範圍第8項之預漬體，其中該成份（c ) 之苯氧基樹脂爲具有聯苯基骨架之苯氧基樹脂者。 10如申請專利範圍第8項或第9項之預漬體，其中該 環氧樹脂組成物加熱硬化後之比誘電率於測定周波數 1 GHz及溫度23 °C之條件下爲Ο 〇 1 5以下者。 1 1如申請專利範圍第8項至第1 0項中任一項之預漬 體，其中該環氧樹脂組成物中成份（A )芳香族系環氧樹 脂之環氧基與成份（B )芳香族系氰酸酯化合物之氰氧基 相互之比例爲1 : 0 5〜1 : 3者，針對1 〇〇重量份之成份（ -29- (3) (3)200400242 A )與成份（B )之總量配合成份（c )苯氧基樹脂爲 3〜40重量份者。 12 —種多層印刷電路板，其特徵係藉由如申請專利範 圍第8項至第Π項之預漬體形成絕緣層者。 1 3 —種多層印刷電路板之製造方法，其特徵係含有藉 由如申請專利範圍第8項至第1 1項之預漬體於加壓及加熱 條件下進行層壓塑料於電路基板及硬化後，形成絕緣層之 ί戔’必要時，以氧化劑進行該絕緣層表面之粗化，藉由電 鑛形成導體層之步驟者。 丄4· 一種多層印刷電路板，其特徵係藉由如申請專利範 ®第1 3項之製造方法所取得者。(1) (1) 200400242 Patent application scope 1 A film for adhesion, characterized in that it contains an epoxy resin composition with the following components (&) ~ (c), forming a layer on the support film, (A ) Aromatic epoxy resin (B) with 2 or more epoxy groups in one molecule Aromatic cyanate ester compound with 2 or more cyano groups in one molecule, and C c) Weight average molecular weight of 5000 to 100 The phenoxy resin of 2,000 is the film for bonding as described in the item of the scope of the patent application, wherein the phenoxy resin of the component (C) is a phenoxy resin having a biphenyl skeleton. 3 If the thin film for bonding according to item 1 or item 2 of the patent application scope, wherein the induced tangent of the epoxy resin composition after heating and hardening is 0.15 or less under the conditions of measuring a cycle number of 1 GHz and a temperature of 23 ° C By. 4 If the thin film for bonding according to item 1 or item 3 of the scope of patent application, the epoxy group of the aromatic epoxy resin of component (A) in the epoxy resin composition and the aromaticity of component (B) The cyanooxy group of the family cyanate compound has a mutual ratio of 1 ·· 0 5 ~ 1 ·· 3, and is based on 1,000 parts by weight of the component (A) and the total amount of the component (C) of benzene. The oxyresin is 3 to 40 parts by weight. 5 — A multilayer printed circuit board characterized in that an insulating layer is formed by using a thin film for bonding as described in the claims 1 to 4 of the patent application. 6 — A method for manufacturing a multilayer printed circuit board, which is characterized in that it contains a film for adhesion by applying a film such as items 1 to 4 of the scope of patent application under pressure and -28- (2) (2) 200400242 under heating conditions After laminating the plastic on the circuit board, peeling the support film if necessary 'After the epoxy resin composition of the laminated plastic on the circuit board is heated and hardened to form an insulating layer, the support film is not peeled off if necessary After that, if necessary, the surface of the insulating layer is roughened with an oxidizing agent, and the conductor layer is formed by electroplating. 7 — A multilayer printed circuit board characterized by being obtained by a manufacturing method as described in the patent application No. 6. 8—A kind of pre-stained body, characterized in that an epoxy resin composition containing the following components (a) to (c) is impregnated into a sheet-like reinforcing substrate made of fibers, (A) has 2 or more rings in one molecule (B) an aromatic cyanate compound having 2 or more cyanooxy groups in one molecule, and (C) a phenoxy resin having a weight average molecular weight of 5000 to 100,000. 9 The prestained body according to item 8 of the scope of patent application, wherein the phenoxy resin of the component (c) is a phenoxy resin having a biphenyl skeleton. 10 The pre-stained body according to item 8 or item 9 of the scope of the patent application, wherein the specific electrical conductivity of the epoxy resin composition after heating and hardening is 〇 〇 1 under the conditions of measuring a cycle number of 1 GHz and a temperature of 23 ° C. The following. 11 The pre-stained body according to any one of items 8 to 10 in the scope of the patent application, wherein the epoxy resin component (A) epoxy group and component (B) of the aromatic epoxy resin in the epoxy resin composition The ratio of the cyanooxy groups of the aromatic cyanate compound to each other is 1: 0 5 to 1: 3, and for the component (-29- (3) (3) 200400242 A) and component (B) of 1,000 parts by weight The total amount of the compound (c) phenoxy resin is 3 to 40 parts by weight. 12 — A multilayer printed circuit board characterized by forming an insulating layer by using a pre-stained body as described in the patent application in the range of items 8 to Π. 1 3-A method for manufacturing a multilayer printed circuit board, which comprises laminating plastics on a circuit board and hardening under pressure and heating by using a pre-stained body such as the scope of application for patents Nos. 8 to 11 After that, if necessary, the surface of the insulating layer is roughened with an oxidizing agent, and the conductor layer is formed by electric ore.丄 4 · A multi-layer printed circuit board whose characteristics are obtained by a manufacturing method such as Patent Application No. 13. -30--30-
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